WO1989005810A1 - Processes for the production of amines - Google Patents

Processes for the production of amines Download PDF

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Publication number
WO1989005810A1
WO1989005810A1 PCT/US1988/004454 US8804454W WO8905810A1 WO 1989005810 A1 WO1989005810 A1 WO 1989005810A1 US 8804454 W US8804454 W US 8804454W WO 8905810 A1 WO8905810 A1 WO 8905810A1
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WIPO (PCT)
Prior art keywords
starting materials
molecular sieves
amine starting
piperazine
molecular sieve
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PCT/US1988/004454
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French (fr)
Inventor
Kurt Damar Olson
Steven William Kaiser
Walter Thoams Reichle
Arthur Roy Doumaux, Jr.
David James Schreck
James Herndon Mccain
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Union Carbide Corporation
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Priority claimed from US07/134,815 external-priority patent/US4973709A/en
Application filed by Union Carbide Corporation filed Critical Union Carbide Corporation
Publication of WO1989005810A1 publication Critical patent/WO1989005810A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/08—Bridged systems

Definitions

  • This invention relates to processes for the production of amines. More specifically, this invention relates to processes for preparing triethylenediamine and/or one or more cyclic or acyclic amines by contacting one or more amine starting materials with one or more molecular sieves. By proper choice of catalysts and/or reaction conditions, the processes of this invention can be varied to alter their selectivity to a number of differing and useful products, including triethylenediamine and substituted triethylenediamines.
  • Triethylenediamine also referred to as 1,4-diazabicyclo[2.2.2] octane or DABCO, is an item of commerce which is used as a catalyst for -OH + OCN- reactions to form the urethane linkage in polyurethanes.
  • Various processes for the production of triethylenediamine are known.
  • triethylenediamine may be produced by the method disclosed in WO 87/03592, published June 18, 1987.
  • triethylenediamine may be produced by bringing an amine compound having a specific amino group into contact with a crystalline metal silicate catalyst wherein the molar ratio of silicon dioxide (SiO 2 ) to an oxide of a trivalent metal (M 2 O 3 :M being a trivalent metal) is 12 or more.
  • European Patent Application No. 0158319 discloses a method for preparing 1,4-diazabicyclo[2.2.2]octanes by contacting acyclic or heterocyclic amines with a high-silica zeolite having a silica to alumina ratio of at least 20 to 1.
  • This invention relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting two or more amine starting materials with one or more molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves, the contacting of the two or more amine starting materials with the one or more molecular sieves being effected under conditions effective to convert at least one of the amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
  • molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves
  • This invention also relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more modified molecular sieves selected from (a) modified silica molecular sieves, (b) modified non-zeolitic molecular sieves, and (c) modified zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more modified molecular sieves being effected under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
  • modified molecular sieves selected from (a) modified silica molecular sieves, (b) modified non-zeolitic molecular sieves, and (c) modified zeolitic molecular sieves
  • This invention further relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more non-zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more non-zeolitic molecular sieves being effected under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
  • This invention yet further relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more molecular sieves being effected in the presence of water or steam and under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
  • molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves
  • this invention relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting two or more amine starting materials with one or more molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves, the contacting of the two or more amine starting materials with the one or more molecular sieves being effected under conditions effective to convert at least one of the amine starting, materials into triethylenediamine and/or one or more cyclic or acyclic amines.
  • molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves
  • this invention also relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more modified molecular sieves selected from (a) modified silica molecular sieves, (b) modified non-zeolitic molecular sieves, and (c) modified zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more modified molecular sieves being effected under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
  • modified molecular sieves selected from (a) modified silica molecular sieves, (b) modified non-zeolitic molecular sieves, and (c) modified zeolitic molecular sieves
  • this invention further relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more non-zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more non-zeolitic molecular sieves being effected under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
  • this invention yet further relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or mo-re amine starting materials with one or more molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more molecular sieves being effected in the presence of water or steam and under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
  • molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves
  • cyclic and acyclic amines include, for example, triethylenediamine, substituted triethylenediamines, pyrazine, substituted pyraz.ines, pyridine, substituted pyridines, piperidine, substituted piperidines, piperazine, substituted piperazines, aminoethylethanolamine, diethanolamine, ethylendiamine, morpholine, substituted morpholines, alkyleneamines, alkanolamines, alkylamines, polyalkylene polyamines, allylamines and the like.
  • the processes of the present invention are useful for the conversion of piperazine to triethylenediamine and/or one or more of pyrazine, substituted pyrazines including methyl/ethyl substituted pyrazines, substituted piperazines including N-ethylpiperazine,
  • the products prepared by the processes of the present invention may include both acyclic and cyclic amines.
  • the cyclic products may include both monocyclic materials, for example substituted piperazines, pyrazines and morpholines, and products containing more than one ring.
  • the products can selectively include triethylenediamine or 1,4-diazabicyclo[2.2.2]octane (DABCO).
  • DABCO 1,4-diazabicyclo[2.2.2]octane
  • the products can selectively include a mixture of 2-methyl-triethylenediamine or 2-methyl-1,4-diazabicyclo[2.2.2] octane (methyl DABCO) and triethylenediamine or 1,4-diazabicyclo[2.2.2]octane (DABCO).
  • methyl DABCO 2-methyl-1,4-diazabicyclo[2.2.2] octane
  • DABCO 1,4-diazabicyclo[2.2.2]octane
  • Multiple methyl homologues of 2-methyl-triethylenediamine may also be produced by the processes of this invention.
  • the preferred catalysts for the above conversions include Silicalite, a microporous form of silica described in U.S. Patent No. 4,061,724 issued December 6, 1977 to R.W. Grose et al., and Silicalite treated with phosphoric acid or phosphoric acid equivalents such as diammonium hydrogen phosphate as described hereinbelow.
  • amine and optionally non-amine starting materials can be used in the processes of this invention.
  • Illustrative amine starting materials include one or more, substituted or unsubstituted, cyclic or acyclic amines such as piperazine, monoethanolamine, alkanolamines, ethylenediamine, propylenediamine, butylenediamine, alkylenediamines, isopropan ⁇ lamine, diisopropanolamine, alkylamines, substituted piperazines, N-(2-hydroxyethyl)piperazine, N-(2-aminoethyl)piperazine, diethanolamine, triethanolamine, substituted morph ⁇ lines, morpholine, diethylenetriamine, triethylenetetraamime, higher polyalkylene polyamines and the like.
  • substituted or unsubstituted, cyclic or acyclic amines such as piperazine, monoethanolamine, alkanolamines, ethylenediamine, propyl
  • Illustrative non-amine starting materials which may be used in combination with amine starting materials include one or more diols such as ethylene glycol, propylene glycol and the like.
  • a preferred embodiment of this invention involves co-feeding piperazine and ethylenediamine to selectively produce triethylenediamine at enhanced reaction rates.
  • the molar ratio of amine and non-amine starting materials used in the processes of this invention can vary over a wide range. The preferred molar ratio of amine and non-amine starting material(s) depends not only on the product ratio desired but also on reaction conditions. Since the product ratio changes with changing conversion, the preferred molar ratio for any desired product mix will change with pressure or temperature or anything else that affects the conversion.
  • Suitable molecular sieves for use in this invention include, for example, the silica molecular sieves, such as Silicalite (U.S. Patent No. 4,061,724), Silicalite II (D. M. Bibby, et al.. Nature, 1979, Vol. 280, pg. 664), and fluoride Silicalite (U.S. Patent No. 4,073,865).
  • silica molecular sieves such as Silicalite (U.S. Patent No. 4,061,724), Silicalite II (D. M. Bibby, et al.. Nature, 1979, Vol. 280, pg. 664), and fluoride Silicalite (U.S. Patent No. 4,073,865).
  • suitable molecular sieves for use in this invention include the non-zeolitic molecular sieves having an empirical chemical composition on an anhydrous basis expressed by the formula:
  • Q represents at least one element present as a framework oxide unit “QO 2 n " with charge “n” where “n” may be -3, -2, -1, 0 or +1;
  • R represents at least one organic templating agent present in the intracrystalline pore system;
  • m represents the molar amount of "R” present per mole of
  • Q w Al x P y Si z (Q w Al x P y Si z )O 2 and has a value from zero to about 0.3; and "w”, "x", “y” and “z” represent the mole fractions of QO 2 n , AlPO 2 -, PO 2 + , SiO 2 , respectively, present as framework oxide units.
  • Q is characterized as an element having a mean "T-O" distance in tetrahedral oxide structures between about 1.51 Angstroms and about 2.06 Angstroms.
  • Q has a cation electronegativity between about 125 kcal/gm-atom to about 310 kcal/gm-atom and "Q" is capable of forming stable Q-O-P, Q-O-Al or Q-O-Q bonds in crystalline three dimensional oxide structures having a "Q-O" bond dissociation energy greater than about 59 kcal/gm-atom at 298°K; and said mole fractions being within the limiting compositional values or points as follows: w is equal to 0 to 98 mole percent; y is equal to 1 to 99 mole percent; x is equal to 1 to 99 mole percent; and z is equal to 0 to 98 mole percent.
  • the "Q” of . the “QAPSO” molecular sieves of formula (I) may be defined as representing at least one element capable of forming a framework tetrahedral oxide and may be one of the elements arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium and zinc.
  • the invention contemplates combinations of the elements as representing Q, and to the extent such combinations are present in the structure of a QAPSO they may be present- in molar fractions of the Q component in the range of 1 to 99 percent thereof. It should be noted that Formula (I) contemplates the non-existence of Q and Si.
  • the operative structure is that of AlPO 4 as discussed below. Where z has a positive value, then the operative structure is that of SAPO, discussed below.
  • the term QAPSO does not perforce represent that the elements Q and S (actually Si) are present.
  • the operative structure is that of the ELAPSO or ELAPO or MeAPO or MeAPSO molecular sieves, as herein discussed.
  • molecular sieves of the QAPSO variety will be invented in which Q will be another element or elements, then it is the intention to embrace the same as a suitable molecular sieve for the practice of this invention.
  • zeolitic molecular. sieves such as chabazite, faujasite, levynite, Linde Type A, gismondine, erionite, sodalite, Linde Type X and Y, analcime, gmelinite, harmontome, mordenite, epistilbite, heulandite, stilbite, edingtonite, mesolite, natrolite, scolecite, thomsonite, brewsterite, laumontite, phillipsite, ZSM-5 (U.S. Patent No. 3,702,886), ZSM-20 (U.S. Patent No.
  • zeolitic molecular sieves employable in the practice of this invention are those reviewed by Flanigen in Pure & Applied Chemistry, Vol. 52. pp. 2191-2211, 1980, including their ion exchanged forms. Zeolite ion exchange is reviewed by D. W.
  • Preferred molecular sieves for use in this invention have a crystalline structure related to the pentasil type.
  • Silica molecular sieves e.g., Silicalite
  • zeolitic molecular sieves e.g., Z5M-5
  • Preferred molecular sieves for use in this invention may have a silicon: aluminum ratio of at least about 6:1, preferably 10:1 or 20:1, and more preferably 40:1 or 60:1 or even greater.
  • Aluminum may be a desired component of the molecular sieves even at very low concentrations.
  • Aluminum present as framework aluminum may be more desirable than non-framework aluminum.
  • the molecular sieves typically contain within their internal pore systems at least one form of the organic templating agents used in their synthesis.
  • the organic moiety is present, at least in part, as a charge-balancing cation, and indeed this is generally the case with as-synthesized molecular sieves prepared from organic-containing reaction systems. It is possible, however, that some or all of the organic moiety is an occluded molecular species in a particular species of molecular sieve.
  • the templating agent and hence the occluded organic species, is too large to move freely through the pore system of the molecular sieve and must be removed by calcining the molecular sieve in air at temperatures of 200° to 700°C, preferably about 350° to about 600°C, to thermally degrade the organic species.
  • the pores of the molecular sieve are sufficiently large to permit transport of the templating agent, particularly if the latter is a small molecule, and accordingly complete or partial removal thereof can be accomplished by conventional desorption procedures, such as hydrotreating or chemical treatment such as solvent extraction, which will be familiar to those skilled in the molecular sieve art.
  • the organic templating agent may be removed in situ by placing the molecular sieve still containing the organic templating agent in the reactor, so that the organic templating agent is removed under reaction conditions.
  • the molecular sieves used in this invention offer an inherent limitation to the transformation of amine starting materials to various amine products.
  • the amine molecule In order to react within the molecular sieve catalyst, the amine molecule should have (i) a kinetic diameter which is less than the limiting aperture of the molecular sieve pore in order to enter the catalyst or (ii) a transition state during the reaction which is not larger than the molecular sieve pore or cavity in order transform in the catalyst.
  • the resulting amine products should have a kinetic diameter less than the limiting aperture of the molecular sieve pore in order to exit the catalyst.
  • non-zeolitic molecular sieves or "NZMS” is defined in the instant invention to include the "SAPO" molecular sieves of U.S. Patent No. 4,440,871 and U.S.. Serial No. 575,745, filed January 31, 1984, "ELAPSO” molecular sieves as disclosed in U.S. Serial No. 600,312, filed April 13, 1984, and certain "AlPO 4 ", "MeAPO”, “FeAPO”, “TAPO” and “ELAPO” molecular sieves, as hereinafter described. Crystalline “AlPO 4 " aluminophosphates are disclosed in U.S. Patent No. 4,310,440 issued January 12, 1982, and in U.S. Serial No.
  • crystalline metal aluminophosphates (MeAPOs where "Me” is Mg, Mn, Co and Zn) are disclosed in U.S. Patent No. 4,567,029, issued January 28, 1986; crystalline ferroaluminophosphates (FeAPOs) are disclosed in U.S. Patent No. 4,554,143, issued November 19, 1985; titanium aluminophosphates (TAPOs) are disclosed in U.S. Patent No. 4,500,651, issued February 19, 1985; certain non-zeolitic molecular sieves (“ELAPO”) are disclosed in EPC Patent Application 85104386.9 (Publication No.
  • ELAPSO MOLECULAR SIEVES "ELAPSO” molecular sieves are described in copending U.S. Serial No. 600,312, filed April 13, 1984, (EPC Publication No. 0159,624, published October 30, 1985, incorporated herein by reference) as crystalline molecular sieves having three-dimensional microporous framework structures of ELO 2 , AlPO 2 , PO 2 , SiO 2 oxide units and having an empirical chemical composition on an anhydrous basis expressed by the formula:
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of "R” present per mole of (EL w Al x P y Si z )O 2 and has a value of from zero to about 0.3
  • EL represents at least one element capable of forming a three dimensional oxide framework, "EL” being characterized as an element having a mean "T-O" distance in tetrahedral oxide structures between about 1.51 Angstroms and about 2.06 Angstroms, "EL” having a cation electronegativity between about 125 Kcal/g-atom to about 310 Kca ⁇ /gm-atom and "EL” being capable of forming stable M-O-P, M-O-Al or M-O-M bonds in crystalline three dimensional oxide structures having a "M-O” bond dissociation energy greater than about 59 kcal/g-atom at 298°K; and "w", "x", "y” and "z” represent the mo
  • the "ELAPSO” molecular sieves are also described as crystalline molecular sieves having three-dimensional microporous framework structures of ELO 2 , AlPO 2 , SiO 2 and PO 2 tetrahedral oxide units and having an empirical chemical composition on an anhydrous basis expressed by the formula:
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of “R” present per mole of (EL w Al x P y Si z )O 2 and has a value of from zero to about 0.3
  • EL represents at least one element capable of forming a framework tetrahedral oxide and is selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium and zinc
  • w", "x", “y” and “z” represent the mole fractions of "EL", aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being within the limiting compositional values or points as follows:
  • CoMnMgAPSO 600.182 April 13, 1984 CoMnMgAPSO 057,648(C) June 9, 1987 CoMnMgAPSO
  • MgAPSO MOLECULAR SIEVES The MgAPSO molecular sieves of U.S. Serial No. 600,180, filed April 13, 1984 have three-dimensional microporous framework structures of MgO 2 -2 , AlO 2 -, PO 2 + and SiO 2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula: mR : (Mg w Al x P y Si z )O 2
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of "R” present per mole of (Mg w Al x P y Si z )O 2 and has a value from zero (0) to about 0.3
  • w, "x", "y” and “z” represent the. mole fractions of magnesium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides and each preferably has a value of at least 0.01.
  • the mole fractions "w”, "x", “y” and “ z” are generally defined as being within the limiting compositional values or points as follows:
  • MgAPSO compositions are generally synthesized by hydrothermal crystallization for an effective time at effective pressures and temperatures from a reaction mixture containing reactive sources, of magnesium, silicon, aluminum and phosphorus, an organic templating, i.e., structure-directing, agent, preferably a compound of an. element of Group VA of the Periodic Table, and may be an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between 50°C and 250°C, and preferably between 100°C and 200°C until crystals of the MgAPSO product are obtained, usually a period of from several hours to several weeks.
  • the crystallization period will be from about 2 hours to about 30 days with it typically being from about 4 hours to about 20 days for obtaining MgAPSO crystals.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • reaction mixture compositions expressed in terms of the molar ratios as follows:
  • R is an organic templating agent
  • a is the amount of organic templating agent "R” and can have a value within the range of from zero (0) to about 6 and is more preferably an effective amount greater than zero to about 6
  • b has a value of from zero (0) to about 500, preferably between about
  • reaction mixture is selected such that the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • TBAOH tetrabutylammonium hydroxide (40 wt. % in water);
  • Pr 2 NH di-n-propylamine;
  • Pr 3 NH tri-n-propylamine;
  • Quin Quinuclidine;
  • MQuin Methyl Quinuclidine hydroxide,
  • the MgAPSO compositions may be prepared by preparing reaction mixtures having a molar composition expressed as: eR: fMgO :hAl 2 O 3 : iP 2 O 5 : gSiO 2 : JH 2 O wherein e, f, g, h, i and j represent the moles of template R, magnesium (expressed as the oxide), SiO 2 , Al 2 O 3 , P 2 O 5 (H 3 PO 4 expressed as P 2 O 5 ) and H 2 O, respectively;
  • reaction mixtures may be prepared by the following representative procedures, designated hereinafter as Methods A, B and C.
  • the reaction mixture is prepared by mixing the ground aluminum source (alipro or CATAPAL) with the H 3 PO 4 and water on a gradual basis with occasional cooling with an ice bath . The resulting mixture is blended until a homogeneous mixture is observed.
  • the aluminum source is CATAPAL
  • the water and H 3 PO 4 are first mixed with the CATAPAL added thereto.
  • the magnesium acetate is dissolved in a portion of the water and is then added followed by addition of the LUDOX-LS.
  • the combined mixture is blended until a homogeneous mixture is observed.
  • the organic templating agent is added to this mixture and blended until a homogeneous mixture is observed.
  • the resulting mixture (final reaction mixture) is placed in a lined (polytetrafluoro- ethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for an effective time. Alternatively, if the digestion temperature is 100°C the final reaction mixture is placed in a lined (polytetrafluoroethylene) screw top bottle for a time. Digestions are typically carried out under autogenous pressure. The products are removed from the reaction vessel, cooled and evaluated as set forth hereinafter.
  • Method B When method B is employed the organic templating agent is di-n-propylamine.
  • the aluminum source, silicon source and one-half of the water are first mixed and blended until a homogeneous mixture is observed.
  • a second solution was prepared by mixing the remaining water, the H 3 PO 4 . and the magnesium acetate. This solution is then added to the above mixture.
  • H 3 PO 4 solution is then added to the above mixture and blended until a homogeneous mixture is observed.
  • the organic templating agent(s) is/are then added and the resulting reaction mixture digested and product recovered as in Method A.
  • Method C is carried out by mixing aluminum isopropoxide, LUDOX LS and water in a blender or by mixing water and aluminum iso-propoxide in a blender followed by addition of the LUDOX LS.
  • H 3 PO 4 and magnesium acetate are then added to the resulting mixture.
  • the organic templating agent is then added to the resulting mixture and digested and product recovered as in Method A.
  • MnAPSO MOLECULAR SIEVES As already mentioned, the MnAPSO molecular sieves are described in U.S. Patent No. 4,686,092 issued August 11, 1987 (incorporated herein by reference). CoAPSO MOLECULAR SIEVES The CoAPSO molecular sieves of U.S. Serial No. 600,174, filed April 13, 1984 have three-dimensional microporous framework structures of CoO 2 -2 , AKO 2 -, PO 2 + and SiO 2 tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
  • CoAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of cobalt, silicon, aluminum and phosphorus, an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and optionally an alkali metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at an effective temperature which is generally between 50°C and 250°C and preferably between 100°C and 200°C until crystals of the CoAPSO product are obtained, usually for an effective time of from several hours to several weeks.
  • the effective crystallization time will be from about 2 hours to about 30 days and typically from about 4 hours to about 20 days.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • R is an organic templating agent
  • a is the amount of organic templating agent “R” and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6
  • "b” has a value of from zero (0) to about 500, preferably between about 2 and 300
  • "w", "x", "y” and “z” represent the mole fractions of cobalt, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
  • the reaction mixture is selected such that the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • CoAPSO compositions may be prepared using numerous reagents.
  • Reagents which may be employed to prepare CoAPSOs include:
  • CoSO 4 cobalt sulfate, (CoSO 4 ⁇ 7H 2 O);
  • TBAOH tetrabutylammonium hydroxide (25 wt % in methanol);
  • CoAPSO compositions may be prepared by preparing reaction mixtures having a molar composition expressed as:
  • e, f, h, i, g and j represent the moles of template R, cobalt (expressed as the oxide), Al 2 O 3 , P 2 O 5 (H 3 PO 4 expressed as P 2 O 5 ), SiO 2 and H 2 O, respectively.
  • the reaction mixtures are prepared by forming a starting reaction mixture comprising the H 3 PO 4 and one half of the water. This mixture is stirred and the aluminum source (Alipro or CATAPAL) added. The resulting mixture is blended until a homogeneous mixture is observed. The LUDOX-LS is then added to the resulting mixture and the new mixture blended until a homogeneous mixture is observed. The cobalt source (e.g., Co(Ac) 2 , Co(SO 4 ) or mixtures thereof) is dissolved in the remaining water and combined with the first mixture. The combined mixture is blended until a homogeneous mixture is observed. The organic templating agent is added to this mixture and blended for about two to four minutes until a homogeneous mixture is observed.
  • Alipro or CATAPAL aluminum source
  • the resulting mixture (final reaction mixture) is placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C, 200°C or 225°C) for a time. Digestions are typically carried out at the autogenous pressure. The products are removed from the reaction vessel and cooled.
  • ZnAPSO MOLECULAR SIEVES The ZnAPSO molecular sieves of U.S. Serial No. 600,170, filed April 13, 1984 comprise framework structures of ZnO 2 -2 , AlO 2 -, PO 2 + and SiO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of "R” present per mole of (Zn w Al x P y Si z )O 2 and has a value of zero to about 0.3
  • w, "x", "y” and “ z” represent the mole fractions of zinc, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides and each has a value of at least 0.01.
  • the mole fractions "w”, "x”, “y” and “z” are generally defined being within the limiting compositional values or points as follows: Mole Fraction
  • ZnAPSO compositions are generally synthesized by hydrothermal crystallization at effective process conditions from a reaction mixture containing active sources of zinc, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element or Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure, at a temperature between 50°C and 250°C, and preferably between 100°C and 200°C until crystals of the ZnAPSO product are obtained, usually a period of from several hours to several weeks.
  • the effective crystallization period is from about 2 hours to about 30 days with typical periods of from about 4 hours to about 20 days being employed to obtain ZnAPSO products.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • reaction mixture composition expressed in terms of the molar ratios as follows:
  • R is an organic templating agent
  • a is the amount of organic templating agent “R” and has a value of from zero, to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6
  • "b” has a value of from zero (0) to about 500, more preferably between about 2 and about 300
  • "w", "x", “y” and “z” represent the mole fractions of zinc, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
  • the reaction mixture is selected such that the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • ZnAPSO compositions are typically prepared using numerous reagents.
  • Reagents which may be employed to prepare ZnAPSOs include:
  • LUDOX-LS is the trade name of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent Na 2 O;
  • ZnAc Zinc Acetate, Zn(C 2 H 3 O 2 ) 2 ⁇ 4H 2 O;
  • TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
  • TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
  • TMAOH Tetramethylammonium hydroxide pentahydrate, (CH 3 ) 4 N0H ⁇ 5H 2 O;
  • TPAOH 40 weight percent aqueous solution of tetrapropylammonium hydroxide, (C 3 H 7 ) 4 NOH;
  • Pr 2 NH Di-n-propylamine,
  • ZnAPSO compositions are typically prepared by forming reaction mixtures having a molar composition expressed as:
  • e, f, g, h, i and j represent the moles of template R, zinc (expressed as the oxide), Al 2 O 3 , P 2 O 5 (H 3 PO 4 expressed as P 2 O 5 ), SiO 2 and H 2 O, respectively.
  • the reaction mixtures are generally prepared by forming a starting reaction mixture comprising the H 3 PO 4 and a portion of the water. This mixture is stirred and the aluminum source added. The resulting mixture is blended until a homogeneous mixture is observed. The LUDOX LS is then added to the resulting mixture and the new mixture blended until a homogeneous mixture is observed. The zinc source (zinc acetate) is dissolved in the remaining water and combined with the first mixture. The combined mixture is blended until a homogeneous mixture is observed. The organic templating agent is added to this mixture and blended for about two to four minutes until a homogeneous mixture is observed.
  • the resulting mixture (final reaction mixture) is placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at an effective temperature for an effective time. Digestions are typically carried out under autogenous pressure. The products are removed from the reaction vessel and cooled.
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of "R” present per mole of (M w Al ⁇ P y Si z )O 2 and has a value of from zero (0) to about 0.3
  • M represents at least two elements selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium and zinc
  • "w", "x", "y” and “z” represent the mole fractions of M, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides.
  • M represents the combination of cobalt and manganese.
  • the mole fractions "w”, "x”, “y”, and “z” are generally defined as being within the limiting compositional values or points as follows:
  • QuinAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of the elements M, aluminum, phosphorus and silicon and preferably an organic templating agent, i.e., structure-directing, agent.
  • the structure-directing agents are preferably a compound of an element of Group VA of the Periodic Table, and may be an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure and at typical effective temperatures between 50°C and 250°C, preferably between 100°C and 200°C, until crystals of the QuinAPSO product are obtained, usually over a period of from several hours to several weeks.
  • Typical effective crystallization times are from about 2 hours to 30 days with from about 4 hours to about 20 days being generally employed to obtain QuinAPSO products.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • reaction mixture composition expressed in terms of the molar ratios as follows:
  • R is an organic templating agent
  • a is the amount of organic templating agent “R” and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6
  • b has a value of from zero (0) to about 500, preferably between about 2 and about 300
  • "w", "x", “y” and “z” represent the mole fractions of elements M, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
  • reaction mixture is selected such that the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • Reagents which may be employed to prepare QuinAPSOs include:
  • LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent of Na 2 O;
  • MnAc Manganese acetate, Mn(C 2 H 3 O 2 ) 2 ⁇ 4H 2 O (for QuinAPSOs containing manganese);
  • CoAc Cobalt Acetate, Co(C 2 H 3 O 2 ) 2 ⁇ 4H 2 O (for QuinAPSOs containing cobalt);
  • TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
  • QuinAPSOs may be prepared by forming a starting reaction mixture by adding H 3 PO 4 and one half of the quantity of water. To this mixture an aluminum isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture a silica (e.g., LUDOX-LS) is added and the .resulting mixture blended (about 2 minutes) until a homogeneous mixture is observed. A second mixture is prepared using manganese acetate (or a appropriate source of another element M) and one half of the remaining water.
  • a third mixture is prepared using cobalt acetate (or a appropriate source of another element M) and one half of the remaining water.
  • the three mixtures are admixed and the resulting mixture blended until a homogeneous mixture is observed.
  • the organic templating agent is then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture is observed, i.e., about 2 to 4 minutes.
  • the pH of the mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at an effective temperature for an effective time. Digestions are typically carried out under autogeneous pressure.
  • CoMnMgAPSO MOLECULAR SIEVES The CoMnMgAPSO senary molecular sieves of U.S. Serial No. 600,182, filed April 13, 1984, and of U.S. Serial No. 057,648 filed June 9, 1987, have three-dimensional microporous framework structures of CoO 2 -2 , MnO 2 -2 , MgO 2 -2 , AlO 2 , PO 2 and SiO 2 tetrahedral oxide units having an empirical chemical composition on an anhydrous basis expressed by the formula:
  • R represents at least one organic templating agent .present in the intracrystalline pore system;
  • m represents the molar amount of “R” present per mole of (Co t Mn u Mg v Al x P y Si z )O 2 and has a value of from zero (0) to about 0.3;
  • t, "u”, “v”, “x”, “y” and “z” represent the mole fractions of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides and each has a value of at least 0.01.
  • the mole fractions "w, "x”, “y” and “z”, where “w” is the sum of "t” + “u” + “v”, are. generally defined as being within the limiting compositional values or points as follows:
  • CoMnMgAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, and preferably an organic templating agent, i.e., structure-directing agent.
  • the structure-directing agents are preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between 50°C and 250°C, and preferably between 100°C and 200°C, until crystals of the CoMnMgAPSO product are obtained, usually over a period of from several hours to several weeks. Typical crystallization times are from about 2 hours to about 30 days with from about 4 hours to about 20 days generally being employed to obtain CoMnMgAPSO products.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • R is an organic templating agent
  • a is the amount of org'anic templating agent "R” and has a value, of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6 and more preferably from greater than zero to about 2
  • "b” has a value of from zero (0) to about 500, preferably between about 2 and about 300
  • "t", "u”, “v”, “x”, “y”, and “z” represent the mole fractions of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
  • reaction mixture is selected such that the mole fractions "w”, "x", “y” and “z”, where "w” is the sum of "t” + “u” + “v”, are generally defined as being within the limiting compositional values or points as follows:
  • CoMnMgAPSO compositions may be prepared by using numerous reagents.
  • Reagents which may be employed to prepare CoMnMgAPSOs include:
  • LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent Na 2 O;
  • H 3 PO 4 aqueous solution which is 85 weight percent phosphoric acid
  • MnAc Manganese acetate, Mn(C 2 H 3 O 2 ) 2 ⁇ 4H 2 O;
  • CoAc Cobalt Acetate; Co(C 2 H 3 O 2 ) 2 ⁇ 4H 2 O;
  • MgAc Magnesium Acetate Mg(C 2 H 3 O 2 ) ⁇ 4H 2 O;
  • TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
  • CoMnMgAPSOs may be prepared by forming a starting reaction mixture by adding H 3 PO 4 and one half of the quantity of water. To this mixture an aluminum isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture a silica (e.g., LUDOX-LS) is added and the resulting mixture blended (about 2 minutes) until a homogeneous mixture is observed.
  • silica e.g., LUDOX-LS
  • Three additional mixtures are prepared using cobalt acetate, magnesium acetate and manganese acetate using one third of the remainder of the water for each mixture.
  • the four mixtures are then admixed and the resulting mixture blended until a homogeneous mixture is observed.
  • An organic templating agent is then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture is observed, i.e., about 2 to 4 minutes.
  • the mixture is then placed in a lined . (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature for a time. Digestions are typically carried out under autogenous pressure.
  • SenAPSO MOLECULAR SIEVES The SenAPSO molecular sieves of U.S. Serial No. 600,183, filed April 13, 1984 have three-dimensional microporous framework structures of MO 2 n , AlO 2 -, PO 2 + and SiO 2 tetrahedral oxide units, where "n" is -3, -2, -1, 0 or +1, and have an empirical chemical composition on an anhydrous basis expressed by the formula: mR : (M w Al ⁇ P y Si z )O 2
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of “R” present per mole of (M w Al x P y Si z )O 2 , and has a value of from zero to about 0.3
  • M represents three elements selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium and zinc
  • "n” may have the aforementioned values depending upon the oxidation state of "M”
  • "w", "x", “y” and “z” represent the mole fractions of elements "M", aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides.
  • the mole fractions "w”, “x”, “y” and “z” are generally defined as being within the limiting compositional values or points as follows, wherein “w” denotes the combined mole fractions of the three
  • each element "M" has a mole fraction of at least 0.01:
  • SenAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of elements "M", aluminum, phosphorus and silicon, and preferably an organic templating, i.e., structure-directing, agent.
  • the structure-directing agents are preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between 50°C and 250°C, and preferably between 100°C and 200°C, until crystals of the SenAPSO product are obtained, usually over a period of from several hours to several weeks.
  • Typical crystallization times are from about 2 hours to about 30 days with from about 4 hours to about 20 days generally being employed to obtain SenAPSO products.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • R is an organic templating agent
  • a is the amount of organic templating agent “R” and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about. 6 and more preferably from greater than zero to about 2
  • "b” has a value of from zero (0) to about 500, preferably between about 2 and about 300
  • "w", "x", “y”, and “z” represent the mole fractions of elements "M", aluminum, phosphorus and. silicon, respectively, and each has a value of at least 0.01, with the proviso that each "M” is present in a mole fraction of at least 0.01.
  • reaction mixture is selected such that the mole fractions "w”, "x", “y” and “ z " are generally defined as being within the limiting compositional values or points as follows: Mole Fraction
  • the SenAPSO molecular sieves are prepared by preparative techniques, and using sources of the elements "M” similar to those described for the other APSO molecular sieves described above and below.
  • the AsAPSO.molecular sieves of U.S. Serial No. 599,808, filed April 13, 1984, and U.S. Serial No. 845,484 filed March 31, 1986 have a framework structure of AsO 2 n , AIO 2 -, PO 2 + and SiO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
  • AsAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of arsenic, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the AsAPSO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 12 hours to about 10 days, have been observed.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • reaction mixture composition expressed in terms of the molar ratios as follows:
  • R is an organic templating agent
  • a is the amount of organic templating agent “R” and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 1.0
  • "b” has a value of from zero (0) -to about 500, preferably between about 2 and about 300, most preferably not greater than about 60
  • "w", "x", “y”- and “z” represent the mole fractions of arsenic, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
  • reaction mixture is selected such that the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • reaction mixtures are those containing from about 1 to about 2 total moles of silicon and arsenic, and from about 1 to about 2 moles of aluminum, per mole of phosphorus.
  • AsAPSO compositions may be prepared by using numerous reagents.
  • Reagents which may be employed to prepare AsAPSOs include:
  • LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 .and 0.1 weight percent Na 2 O;
  • TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
  • AsAPSOs may be prepared by forming a starting reaction mixture by dissolving the arsenic (V) oxide and the H 3 PO 4 in at least part of the water. To this solution the aluminum isopropoxide or CATAPAL is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture the templating agent and then the silica is added and the resulting mixture blended until a homogeneous mixture is observed. The mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
  • BAPSO MOLECULAR SIEVES The BAPSO molecular sieves of U.S. Serial No. 600,177, filed April 13, 1984, and U.S. Serial No. 845,255 filed March 28, 1986 have a framework structure of BO 2 -, AlO 2 -, PO 2 + and SiO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of "R” present per mole of (B w Al x P y Si z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
  • w, "x", "y” and “z” represent the mole fractions of the elements boron, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides.
  • the mole fractions "w”, "x” , "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • the values of w, x, y and z are as follows:
  • BAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of boron, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the BAPSO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 20 days, have been observed.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • reaction mixture composition expressed in terms of the molar ratios as follows:
  • R is an organic templating agent
  • a is the amount of organic templating agent "R” and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 0.5
  • "b” has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably not greater than about 20
  • "w", "x", "y” and “z” represent the mole fractions of boron, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
  • the reaction mixture is selected such that the mole fractions "w”, "x”, “y” and “z” are generally defined as being within the limiting compositional values or points as follows
  • reaction mixtures are those containing from about 1.0 to about 2 total moles of silicon and boron, and from about 0.75 to about 1.25 moles of aluminum, per mole of phosphorus.
  • Molecular sieves containing boron, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:
  • BAPSO compositions may be prepared by using numerous reagents.
  • Reagents which may be employed to prepare BAPSOs include:
  • CATAPAL Trademark of Condea Corporation for hydrated pseudoboehmite
  • LUDOX-LS LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent Na 2 O;
  • TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
  • TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
  • BAPSOs may be prepared by forming a starting reaction mixture by dissolving aluminum isopropoxide in an alcohol such as isopropanol, adding the H 3 PO 4 and recovering the solid which precipitates.
  • This solid is then added to water, and trialkylborate (for example trimethyl borate) added, followed by silica and the templating agent.
  • This mixture is then blended until a homogeneous mixture is observed.
  • the mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel. and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
  • BeAPSO MOLECULAR SIEVES The BeAPSO molecular sieves of U.S. Serial No. 600,176, filed April 13, 1984, and U.S. Serial No. 841,752 filed March 20, 1986 have a framework structure of BeO 2 -2 , AlO 2 -, PO 2 + and SiO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of "R” present per mole of (Be w Al x P y Si z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
  • w, "x", "y” and “z” represent the mole fractions of the elements beryllium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides.
  • the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • the values of w, x, y and z are as follows:
  • BeAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of beryllium, silicon, aluminum and phosphorus, preferrably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under. autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the BeAPSO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 20 days, have been observed, with from 1 to 10 days being preferred.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • reaction mixture composition expressed in terms of the molar ratios as follows:
  • R is an organic templating agent
  • a is the amount of organic templating agent “R” and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 0.5
  • "b” has a value of from zero (0) to about 500, preferably between about 2 to about 300, most preferably not greater than about 20
  • "w", "x", “y” and “z " represent the mole fractions of beryllium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01,
  • reaction mixture is selected such that the mole fractions "w”, "x", “y” and “ z" are generally defined as being within the limiting compositional values or points as follows:
  • BeAPSO compositions may be prepared by using numerous reagents.
  • Reagents which may be employed to prepare BeAPSOs include:
  • CATAPAL Trademark of Condea Corporation for hydrated pseudoboehmite
  • LUDOX-LS LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent Na 2 O;
  • TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
  • TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
  • BeAPSOs may be prepared by forming a starting solution by mixing H 3 PO 4 in at least part of the water. To this solution is added beryllium sulfate (or another beryllium salt) and the resultant mixture stirred until a homogeneous solution is obtained. To this solution may be added successively the aluminum oxide, the silica and the templating agent, with the mixture being stirred . between each addition until it is homogeneous. Themixture is then placed in a lined (polytetra- fluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
  • CAPSO MOLECULAR SIEVES The CAPSO molecular sieves of U.S. Serial No. 599,830, filed April 13, 1984, and U.S. Serial No. 852,174 filed April 15, 1986 have a framework structure of CrO 2 n , AIO 2 -, PO 2 + and SiO 2 tetrahedral units (where "n" is -1, 0 or +1) having an empirical chemical composition on an anhydrous basis expressed by the formula:
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of “R” present per mole of (Cr w Al x P y Si z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
  • w, "x” , "y” and “z” represent the mole fractions of the elements chromium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides.
  • the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • the values of x and y in the above formula are each within the range of about 0.4 to 0.5 and (z+w) is in the range of about 0.02 to 0.15. Since the exact nature of the CAPSO molecular sieves is not clearly understood at present, although all are believed to contain CrO 2 tetrahedra in the three-dimensional microporous crystal framework structure, it is advantageous to characterize the CAPSO molecular sieves by means of their chemical composition. This is due to the low level of chromium present in certain of the CAPSO molecular sieves prepared to date which makes it difficult to ascertain the exact nature of the interaction between chromium, aluminum, phosphorus and silicon.
  • CAPSO compositions are generally synthesized by hydrothermal crystallization from- a reaction mixture containing reactive sources of chromium, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the CAPSO product are obtained, usually a period of from several hours to several weeks.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • reaction mixture composition expressed in terms of the molar ratios as follows:
  • R is an organic templating agent
  • a is the amount of organic templating agent "R” and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 0.5
  • "b” has a value of from zero (0). to about 500, preferably between about 2 and about 300, most preferably not greater than about 20
  • "w", "x", "y” and " z " represent the mole fractions of chromium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
  • reaction mixture is selected such that the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • reaction mixtures are those containing from about 0.3 to about 0.5 total moles of silicon and chromium, and from about 0.75 to about 1.25 moles of aluminum, per mole of phosphorus.
  • CAPSO compositions may be prepared by using numerous reagents.
  • Reagents which may be employed to prepare CAPSOs include:
  • LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent Na 2 O;
  • TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
  • TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
  • CAPSOs may be prepared by forming a starting solution by dissolving H 3 PO 4 in at least part of the water. To this solution the aluminum isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture the silica, the chromium acetate or chromium acetate hydroxide and the templating agent are successively added and at each step the resulting mixture is blended until a homogeneous mixture is observed.
  • the water and aluminum isopropoxide may first be mixed, and then the silica, the chromium acetate or chromium acetate hydroxide, the. phosphoric acid and the templating agent added, and .again at each step the resulting mixture is blended until a homogeneous mixture is observed.
  • the mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
  • GaAPSO MOLECULAR SIEVES The GaAPSO molecular sieves of U.S. Serial No. 599,925, filed April 13, 1984, and U.S. Serial No. 845,985 filed March 31, 1986 have a framework structure of GaO 2 -, AlO 2 -, PO 2 + and SiO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of "R” present per mole of (Ga w Al x P y Si z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.2
  • w, "x", "y” and “z” represent the mole fractions of the elements gallium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides.
  • the mole fractions "w”, "x”, “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • the.values of w, x, y and z are as follows:
  • GaAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of gallium, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the GaAPSO product are obtained, usually a period of from several hours to several weeks.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • reaction mixture composition expressed in terms of the molar ratios as follows: aR : (Ga w Al x P y Si z )O 2 : bH 2 O
  • R is an organic templating agent
  • a is the amount of organic templating agent “R” and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 1.0
  • "b” has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably not greater than about 20
  • "w", "x", “y” and “z” represent the mole fractions of gallium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
  • reaction mixture is selected such that the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • reaction mixtures are those containing from about 0.5 to about 1.0 total moles of silicon and gallium, and from about 0.75 about 1.25 moles of aluminum, per mole of phosphorus.
  • GaAPSO compositions may be prepared by using numerous reagents.
  • Reagents which may be employed to prepare GaAPSOs include:
  • LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent Na 2 O;
  • TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
  • GaAPSOs may be prepared by forming a starting solution by dissolving H 3 PO 4 in at least part of the water. To this solution the aluminum hydroxide or isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture is added a second solution prepared by adding silica to a solution containing the gallium hydroxide and the templating agent and then the combined mixture is blended until a homogeneous mixture is observed.
  • the templating agent may be added to the solution containing the phosphoric acid and water, and a solution of gallium sulfate in water added, followed by successive additions of silica and aluminum oxide and then the combined mixture is blended until a homogeneous mixture is observed.
  • the mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
  • GeAPSO MOLECULAR SIEVES The GeAPSO molecular sieves of U.S. Serial No. 599,971, filed April 13, 1984, and U.S. Serial No. 852,175 filed April 15, 1986 have a framework structure of GeO 2 , AlO 2 -, PO 2 + and SiO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of "R” present per mole of (Ge w Al ⁇ P y Si z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
  • w, "x", "y” and “z” represent the mole fractions of the elements geranium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides.
  • the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limited compositional values or points as follows:
  • the values of w, x, y and z are as follows:
  • the values of w, x, y and z are as follows:
  • GeAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of geranium, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the GeAPSO product are obtained, usually a period of from several hours to several weeks.
  • Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 20 days, and preferably about 12 hours to about 7 days have been observed.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • reaction mixture composition expressed in terms of the molar ratios as follows:
  • R is an organic templating agent
  • a is the amount of organic templating agent “R” and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 0.5
  • "b” has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably not greater than about 20; and desirably not greater than about 10
  • "w", "x", “y” and “z” represent the mole fractions of germanium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
  • reaction mixture is selected such that the mole fractions "w”, "x” , “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • reaction mixtures are those containing from about 0.2 to about 0.3 total moles of silicon and germanium, and from about 0.75 about 1.25 moles of aluminum, per mole of phosphorus.
  • GeAPSO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare GeAPSOs include:
  • LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent Na 2 O;
  • TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
  • TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
  • Preparative Procedures it may be advantageous, when synthesizing the GeAPSO compositions, to first combine sources of germanium and aluminum, or of germanium, aluminum and silicon, to form a mixed germanium/aluminum or germanium/aluminum/silicon compound (this compound being typically a mixed oxide) and thereafter to combine this mixed compound with a source of phosphorus to form the final GeAPSO composition.
  • Such mixed oxides may be prepared for example by hydrolyzing aqueous solutions containing germanium tetrachloride and aluminum chlorhydrol, or germanium ethoxide, tetraethylorthosilicate, and aluminum tri-sec-butoxide.
  • GeAPSOs may be prepared by forming a starting solution by dissolving H 3 PO 4 in at least part of the water. To this solution the aluminum isopropoxide or CATAPAL is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture is the templating agent and then a solution containing tetraethylorthosilicate and germanium ethoxide, and the resulting mixture blended until a homogeneous mixture is observed.
  • the phosphoric acid may first be mixed with the templating agent, and then a solution containing tetraethylorthosilicate and germanium ethoxide combined with the phosphoric acid/templating agent solution. Then the aluminum oxide is added and the resultant mixture blended until homogeneous.
  • the phosphoric acid may first be mixed with the templating agent and water, and to the resultant solution is added the solid aluminum/ silicon/germanium mixed oxide prepared as described above. The resultant mixture is then blended until homogeneous.
  • the final mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
  • LiAPSO MOLECULAR SIEVES The LiAPSO molecular sieves of U.S. Serial No. 599,952, filed April 13, 1984, and U.S. Serial No. 847,227 filed April 2, 1986 have a framework structure of LiO 2 -3 , AlO 2 -, PO 2 + and SiO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: mR : (Li w Al ⁇ P y Si z )O 2
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of "R” present per mole of (Li w Al ⁇ P y Si z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
  • w, "x” , "y” and “z” represent the mole fractions of the elements lithium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides.
  • the mole fractions "w”, "x”, “y” and “z” are generally defined as being within the limiting compositional values or points, as follows:
  • the. values of w, x, y and z are as follows:
  • the value of w+z is not greater than about 0.20. Since the exact nature of the LiAPSO molecular sieves is not clearly understood at present, although all are believed to contain LiO 2 tetrahedra in the three-dimensional microporous crystal framework structure, it is advantageous to characterize the LiAPSO molecular sieves by means of their chemical composition. This is due to the low level of lithium present in certain of the LiAPSO molecular sieves prepared to date which makes it difficult to ascertain the exact nature of the interaction between lithium, aluminum, phosphorus and silicon.
  • LiO 2 tetrahedra are substituted isomorphously for AlO 2 , PO 2 or SiO 2 tetrahedra, it is appropriate to characterize certain LiAPSO compositions by reference to their chemical composition in terms of the mole ratios of oxides.
  • LiAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of lithium, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the LiAPSO product are obtained, usually a period of from several hours to several weeks.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • reaction mixture composition expressed in terms of the molar ratios as follows :
  • R is an organic templating agent
  • a is the amount of organic templating agent “R” and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 0.5
  • "b” has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably not greater than about 20, and most desirably not greater than about 10
  • "w", "x", “y” and “ z” represent the mole fractions of lithium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
  • reaction mixture is selected such that the mole fractions "w”, "x", “y” and “ z " are generally defined as being within the limiting compositional values or points as follows: Mole Fraction
  • LiAPSO compositions may be prepared by using numerous reagents.
  • Reagents which may be employed to prepare LiAPSOs include:
  • LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent Na 2 O;
  • LiAPSOs may be prepared by forming a starting reaction mixture mixing lithium phosphate and aluminum oxide, then adding the resultant mixture to the H 3 PO 4 . To the resultant mixture is added silica and the templating agent and the resulting mixture is blended until a homogeneous mixture is observed. The mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
  • AlPO 4 aluminophosphate molecular sieves are described in U.S. Patent No. 4,310,440 (incorporated herein by reference); these AlPO 4 molecular sieves are also described in U.S. Serial No. 880,559, filed June 30, 1986.
  • MeAPO MOLECULAR SIEVES MeAPO molecular sieves are crystalline microporous aluminophosphates in which the substituent metal is one of a mixture of two or more divalent metals of the group magnesium, manganese, zinc and cobalt and are disclosed in U.S. Patent No. 4,567,029 (incorporated herein by reference).
  • ferroaluminophosphates are disclosed in U.S. Patent No. 4,554,143 (incorporated herein by reference).
  • TAPO MOLECULAR SIEVES As already mentioned, TAPO molecular sieves are disclosed in U.S. Patent No. 4,500,561 (incorporated herein by reference).
  • ELAPO MOLECULAR SIEVES "ELAPO” molecular sieves are a class of crystalline molecular sieves in which at least one element capable of forming a three-dimensional microporous framework forms crystal framework structures of AlO 2 -, PO 2 + and MO 2 n tetrahedral oxide units wherein "MO 2 n " represents at least one different element (other than Al or P) present as tetrahedral oxide units "MO 2 n " with charge "n” where "n” may be -3, -2, -1, 0 or +1.
  • the members of this novel class of molecular sieve compositions have crystal framework structures of AlO 2 -, PO 2 + and MO 2 n tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of “R” present per mole of (M x Al y P z )O 2
  • M represents at least one element capable of forming framework tetrahedral oxides
  • x, "y” and “z” represent the mole fraction of "M” , aluminum and phosphorus, respectively, present as tetrahedral oxides.
  • M is at least one different (i.e., not aluminum, phosphorus or oxygen) element such that the molecular sieves contain at least one framework tetrahedral unit in addition to AIO 2 - and PO 2 + .
  • M is at least one element selected from the group consisting of arsenic, beryllium, boron, cobalt, chromium, gallium, germanium, iron, lithium, magnesium, manganese, titanium and zinc, subject to certain restrictions on the combinations of elements as will appear from the discussions of individual groups of ELAPOs below.
  • ELAPOs and their preparation are disclosed in European Patent Application Serial No. 85104386.9, filed April 11, 1985 (EPC Publication No. 0158976, published October 13, 1985, incorporated herein by reference) and 85104388.5, filed April 11, 1985 (EPC Publication No. 158349, published October 16, 1985, incorporated herein by reference).
  • ESAPO electroactive polystyrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-S-S-S-s
  • ElAPO (M comprises two different
  • ELAPO ELAPO molecular sieves
  • ELAPO ELAPO molecular sieves
  • M element (s) "M” in a framework of AlO 2 -, PO 2 + and Mo 2 n tetrahedral oxide units.
  • ELAPO element (s) "M” in a framework of AlO 2 -, PO 2 + and Mo 2 n tetrahedral oxide units.
  • EL element
  • MgBeAPO designates a molecular sieve comprised of AlO 2 -, PO 2 + , MgO 2 -2 and BeO 2 -2 tetrahedral units.
  • each species is assigned a number and is identified as "ELAPO-i" wherein "i” is an integer.
  • the given species designation is not intended to denote a similarity in structure to any other species denominated by a similar identification system.
  • the ELAPO molecular sieves comprise at least one additional element capable of forming framework tetrahedral oxide units (MO 2 n ) to form crystal framework structures with AlO 2 - and PO 2 + tetrahedral oxide uni.ts wherein "M” represents at least one element capable of forming tetrahedral units "MO 2 n " where "n” is -3, -2,
  • -1, 0 or +1 is at least one element selected from the group consisting of arsenic, beryllium, boron, cobalt, chromium, gallium, germanium, iron, lithium, magnesium, manganese, titanium and zinc.
  • the ELAPO molecular sieves have crystalline three-dimensional microporous framework structures of AlO 2 -, PO 2 + and MO 2 n tetrahedral units and have an empirical chemical composition, on an anhydrous basis expressed by the formula: mR : (M x Al y P z )O 2 ;
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of “R” present per mole of (M x Al y P z )O 2 and has a value of zero to about 0.3
  • M represents at least one element capable of forming framework tetrahedral oxides where "M” is at least one element selected from the group consisting of arsenic, beryllium, boron, cobalt, chromium, gallium, germanium, iron, lithium, magnesium, manganese, titanium and zinc.
  • the relative amounts of element (s) "M", aluminum and phosphorous are expressed by the empirical chemical formula (anhydrous):
  • the ELAPO molecular sieves have crystalline three-dimensional microporous framework structures of MO 2 n , AlO 2 - and PO 2 + tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: mR : (M ⁇ Al y P z )O 2
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents a molar amount of “R” present per mole of (M x Al y P z )O 2 and has a value of zero to about 0.3
  • M represents at least one different element (other than Al or P) capable of forming framework tetrahedral oxides, as hereinbefore defined
  • x, "y” and “z” represent the mole fractions of "M", aluminum and phosphorous, respectively present as tetrahedral oxides
  • said mole fractions "x” , “y” and “z” are within the following values for "x", “y” and “z", although as will appear hereinbelow, the limits for "x”, “y” and “z” may vary slightly with the nature of the element “M” :
  • ELAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of the elements "M", aluminum and phosphorous, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between 50°C and 250°C, and preferably between 100°C and 200°C, until crystals of the ELAPO product are obtained, usually a period of from several hours to several weeks. Typical crystallization times are from about 2 hours to about 30 days with from about 2 hours to about 20 days being generally employed to obtain crystals of the ELAPO products.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • reaction mixture composition expressed in terms of the molar ratios as follows:
  • R is an organic templating agent
  • a is the amount of organic templating agent “R” and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6
  • "b” has a value of from zero (0) to about 500, preferably between about 2 and 300
  • M represents at least one element, as above described, capable of forming tetrahedral oxide framework units, MO 2 n , with AlO 2 - and PO 2 + tetrahedral units
  • "n” has a value of -3, -2, -1, 0 or +1
  • "x", "y” and “z” represent the mole fractions of "M", aluminum and phosphorous, respectively; "y” and “z” each have a value of at least 0.01 and "x” has a value of at least 0.01 with each element "M” having a mole fraction of at least 0.01.
  • This latter form is readily converted to the former form by routine calculations by dividing the total number of moles of "M”, aluminum and phosphorous into the moles of each of "M", aluminum and phosphorous.
  • the moles of template and water are similarly normalized by dividing by the total moles of "M", aluminum and phosphorous.
  • the organic templating agent can be any of those heretofore proposed for use in the synthesis of conventional zeolite aluminosilicates.
  • these compounds contain elements of Group VA of the Periodic Table of Elements, particularly nitrogen, phosphorous, arsenic and antimony, preferably nitrogen or phosphorous and most preferably nitrogen, which compounds also contain at least one alkyl or aryl group having from 1 to 8 carbon atoms.
  • templating agents are the amines, quaternary phosphonium compounds and quaternary ammonium compounds, the latter two being represented generally by the formula R 4 X + wherein "X" is nitrogen or phosphorous and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms.
  • Polymeric quaternary ammonium salts such as [(C 14 H 32 N 2 ) (OH) 2 ] ⁇ wherein "x" has a value of at least 2 are also suitably employed.
  • the mono-, di- and tri-amines are advantageously utilized, either alone or in combination with a quaternary ammonium compound or other templating compound. Mixtures of two or more templating agents can either produce mixtures of the desired ELAPOs or the more strongly directing templating species may control the course of the reaction with the other templating species serving primarily to establish the pH conditions of the reaction gel.
  • Representative templating agents include tetramethylammonium, tetraethylammonium, tetrapropylammonium or tetrabutylammonium ions; tetrapentylammonium ion; di-n-propylamine; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methylpyridine; N,N-dimethylbenzylamine; N,N-dimethylethanolamine; choline; N,N'-dimethyl ⁇ i ⁇ erazine; 1,4-diazabicyclo (2,2,2,) octane; N-methyldiethanolamine; N-methylethanolamine; N-methylpiperidine; 3-methyl ⁇ i ⁇ eridine; n-methylcyclohexylamine; 3-methyl ⁇ yridine; 4-methyl ⁇ yridine; quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,
  • the phosphorous source is preferably phosphoric acid, but organic phosphates such as triethyl phosphate may be satisfactory, and so also may crystalline or amorphous aluminophosphates such as the AlPO 4 composition of U.S. P. 4,310,440.
  • Organophosphorous compounds such as tetrabutylphosphonium bromide, do not apparently serve as reactive sources of phosphorous, but these compounds may function as templating agents.
  • Conventional phosphorous salts such as sodium metaphosphate, may be used, at least in part, as the phosphorous source, but are not preferred.
  • the aluminum source is preferably either an aluminum alkoxide, such as aluminum isopropoxide, or pseudoboehmite.
  • the crystalline or amorphous aluminophosphates which are a suitable source of phosphorous are, of course, also suitable sources of aluminum.
  • the element (s) "M” can be introduced into the reaction system in any form which permits the formation in situ of reactive form of the element, i.e., reactive to form the framework tetrahedral oxide unit of the element.
  • the organic and inorganic salts, of "M” such as oxides, alkoxides, hydroxides, halides and carboxyates, may be employed including the chlorides, bromides, iodides, nitrates, sulfates, phosphates, acetates, formates, and alkoxides, including ethoxides, propoxides and the like. Specific preferred reagents for introducing various elements "M” are discussed hereinbelow.
  • the as-synthesized ELAPO generally contains within its internal pore system at least one form of the templating agent employed in its formation.
  • the organic moiety is present, at least in part, as a charge-balancing cation as is generally the case with as-synthesized aluminosilicate zeolites prepared from organic-containing reaction systems. It is possible, however, that some or all of the organic moiety is an occluded molecular species in a particular ELAPO species.
  • the templating agent and hence the occluded organic species, is too large to move freely through the pore system of the ELAPO product and must be removed by calcining the ELAPO at temperatures of 200°C to 700°C to thermally degrade the organic species.
  • the pores of the ELAPO product are sufficiently large to permit transport of the templating agent, particularly if the latter is a small molecule, and accordingly complete or partial removal thereof can be accomplished by conventional desorption procedures such as carried out in the case of zeolites.
  • the present ELAPO compositions are formed from MO 2 n , AlO 2 - and PO 2 + tetrahedral oxide units which, respectively, have a net charge of "n", (where "n" may be -3, -2, -1, 0 or +1), the matter of cation exchangeability is considerably more complicated than in the case of zeolitic molecular sieves in which, ideally, there is stoichiometric relationship between AlO 2 - tetrahedra and charge-balancing cations.
  • an AlO 2 - tetrahedron can be balanced electrically either by association with a PO 2 + tetrahedron or a simple cation such as an alkali metal cation, a proton (H + ), a cation of "M" present in the reaction mixture, or an organic cation derived from the templating agent.
  • an MO 2 n tetrahedron where "n" is negative, can be balanced electrically by association with PO 2 + tetrahedra, a cation of "M” present in the reaction mixture, organic cations derived from the templating agent, a simple cation such as an alkali metal cation, or other divalent or polyvalent metal cation, a proton (H + ), or anions of cations introduced from an extraneous source. It has also been postulated that non-adjacent AlO 2 - and PO 2 + tetrahedral pairs can be balanced by Na + and OH- respectively (Flanigen and Grose, Molecular Sieve Zeolites-I, ACS, Washington, D.C. (1971).
  • the AsAPO molecular sieves of U.S. Serial No. 600,166, filed April 13, 1984, and U.S. Serial No. 830,889 filed February 19, 1986 have a framework structure of AsO 2 n , AlO 2 - and PO 2 + tetrahedral units (where "n" is -1 or +1) and have an empirical chemical composition on an anhydrous basis expressed by the formula:
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of "R present per mole of (As x Al y P z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
  • x, "y” and “z” represent the mole fractions of the elements arsenic, aluminum and phosphorous, respectively, present as tetrahedral oxides.
  • the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • AsAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of arsenic, aluminum and phosphorous, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, .preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the AsAPO product are obtained, usually a period of from several hours to several weeks.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • reaction mixture composition expressed in terms of the molar ratios as follows:
  • R is an organic templating agent
  • a is the amount of organic templating agent “R” and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 0.5
  • "b” has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably not greater than about 20
  • "x", "y” and “z” represent the mole fractions of arsenic, aluminum and phosphorous, respectively, and each has a value of at least 0.01.
  • reaction mixture is selected such that the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • Especially preferred reaction mixtures are those wherein the mole fractions "x", "y” and “z” are within the limiting compositional values or points as follows:
  • AsAPO compositions may be prepared by using numerous reagents.
  • Reagents which may be employed to prepare AsAPOs include:
  • TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
  • TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
  • AsAPOs may be prepared by forming a starting reaction mixture by dissolving the arsenic (V) oxide and the H 3 PO 4 in at least part of the water. To this solution the aluminum oxide or isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture the templating agent and the resulting mixture blended until a homogeneous mixture is observed.
  • the mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
  • BAPO MOLECULAR SIEVES The BAPO molecular sieves of U.S. Serial No. 599,812, filed April 13, 1984, U.S. Serial No. 804,248, filed December 4, 1985, and U.S. Serial No. 029,540, filed March 24, 1987, have a framework structure of BO 2 -, AlO 2 - and PO 2 + tetrahedral units and have an empirical chemcial composition on an anhydrous basis expressed by the formula:
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of "R” present per mole of (B x Al y P z )O 2 and has a value of zero to about 0.3
  • x", "y” and “z” represent the mole fractions of the elements boron, aluminum and phosphorus, respectively, present as tetrahedral oxides.
  • the more fractions "x”, “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • the values of x, y, and z are within the limiting compositional values or points as follows:
  • BAPO molecular sieves are those in which the mole fraction, "x", of boron is not greater than about 0.3.
  • BAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of boron, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal .
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the BAPO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 14 days, and preferably about 1 to about 7 days, have been observed.
  • the product is recovered by any conveniently method such as centrifugation or filtration.
  • reaction mixture composition expressed in terms of the molar ratios as follows:
  • R is an organic templating agent
  • a is the amount of organic templating agent “R” and is an effective amount preferably within the range of greater than zero (0) to about 6, and most preferably not more than about 1.0
  • "b” has a value of from zero (0) to about 500, ' preferably between about 2 and about 300, desirably not greater than about 20, and most desirably not greater than about 10
  • "x", "y” and “z” represent the mole fractions of boron, aluminum and phosphorus, respectively, and each has a value of at least 0.01.
  • reaction mixture is selected such that the . mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • reaction mixtures are those containing from 0.5 to 2.0 moles of B 2 O 3 and from 0.75 to 1.25 moles of Al 2 O 3 for each mole of P 2 O 5 .
  • BAPO molecular sieves The exact nature of the BAPO molecular sieves is not entirely understood at present, although all are believed to contain BO 2 , AlO 2 and PO 2 tetrahedra in the three-dimensional microporous framework structure.
  • the low level of boron present in some of the instant molecular sieves makes it difficult to ascertain the exact nature of the interactions among boron, aluminum and phosphorus.
  • BO 2 tetrahedra are present in the three-dimensional microporous framework structure, it is appropriate to characterize certain BAPO compositions in terms of the molar ratios of oxides.
  • Molecular sieves containing boron, aluminum and phosphorus as framework tetrahedral oxide units are prepared as follows:
  • BAPO compositions may be prepared by using numerous reagents.
  • Reagents which may be employed to prepare BAPOs include:
  • TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
  • TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
  • Pr 3 N tri-n-propylamine, (C 3 H 7 ) 3 N;
  • TMAOH tetramethylammonium hydroxide
  • TPAOH tetrapropylarnmonium hydroxide
  • Preparative Procedures In the preferred method of synthesizing the BAPO compositions, one first combines sources of boron, aluminum and phosphorus to form an amorphous material containing all three elements, and thereafter heats the amorphous material to produce a crystalline BAPO molecular sieve. It is not necessary that the total quantities of the reactive sources of boron, aluminum and phosphorus to be used in the final reaction mixture be present in the amorphous material, since additional quantities of the elements can be added during the later heat treatment; in particular, it has been found convenient to add additional quantities of phosphorus to the amorphous material before the heat treatment. The preliminary formation of the amorphous material assists in the incorporation of the boron into the final molecular sieve.
  • BAPOs may be prepared by forming a solution of boric acid in a methanolic solution of the templating agent, then adding a hydrated aluminosphosphate and water and stirring to form a homogeneous reaction slurry. This slurry is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
  • BeAPO MOLECULAR SIEVES The BeAPO molecular sieves of U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984,
  • No. 835,293 filed March 3, 1986 have a framework structure of BeO 2 -2 , AlO 2 - and PO 2 + tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of "R” present per mole of (Be x Al y P z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
  • x, "y” and “z” represent the mole fractions of the elements beryllium, aluminum and phosphorus, respectively, present as tetrahedral oxides.
  • the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows: Mole Fraction
  • the values of x, y and z are within the limiting compositional values or points as follows:
  • BeAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of beryllium, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • a reaction mixture containing reactive sources of beryllium, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • the reaction mixture is generally placed in a .sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250oC, and preferably between about 100°C and about 200°C until crystals of the BeAPO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 14 days, and preferably about 1 to about 7 days, have been observed.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • reaction mixture composition expressed in terms of the molar ratios as follows:
  • R is an organic templating agent
  • a is the amount of organic templating agent “R” and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 1.5
  • "b” has a value of from zero (0) to about 500, preferably between about .2 and about 300, most preferably not greater than about 50
  • "x", "y” and “z” represent the mole fractions of beryllium, aluminum and phosphorus, respectively, and each has a value of at least 0.01.
  • reaction mixture is selected such that the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • Especially preferred reaction mixtures are those wherein the mole fractions "x", "y” and “z” are within the limiting compositional values or points as follows:
  • BeAPO compositions may be prepared by using numerous reagents.
  • Reagents which may be employed to prepare BeAPOs include:
  • TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
  • BeAPOs may be prepared by forming a starting reaction mixture by dissolving the beryllium sulfate and the H 3 PO 4 in at least part of the water. To this solution the aluminum oxide or isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture the templating agent and the resulting mixture blended until a homogeneous mixture is observed. The mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
  • CAPO MOLECULAR SIEVES The CAPO molecular sieves, of U.S. Serial No. 599,813, filed April 13, 1984, and U.S. Serial No. 830,756 filed February 19, 1986 have a framework structure of CrO 2 n , AlO 2 - and PO 2 + tetrahedral units (where "n" is -1, 0 or +1) and have an empirical chemical composition on an anhydrous basis expressed by the formula
  • CAPO molecular sieves Since the exact nature of the CAPO molecular sieves is not clearly understood at present, although all are believed to contain CrO 2 tetrahedra in the three-dimensional microporous crystal framework structure, it is advantageous to characterize the CAPO molecular sieves by means of their chemical composition. This is due to the low level of chromium present in certain of the CAPO molecular sieves prepared to date which makes it difficult to ascertain the exact nature of the interaction between chromium, aluminum and phosphorous. As a result, although it is believed that CrO 2 tetrahedra are substituted isomorphously for AlO 2 or PO 2 tetrahedra, it is appropriate to. characterize certain CAPO compositions by reference to their chemical composition in terms of the mole ratios of oxides.
  • CAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of chromium, aluminum and phosphoro.us, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the CAPO product are obtained, usually a period of from several hours to several weeks.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • reaction mixture composition expressed in terms of the molar ratios as follows:
  • R is an organic templating agent
  • a is the amount of organic templating agent "R” and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 0.6
  • b has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably not greater than about 20
  • x, "y” and “z” represent the mole fractions of chromium, aluminum and phosphorous, respectively, and each has a value of at least 0.01.
  • reaction mixture is selected such that the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • reaction mixtures are those containing from about 0.1 to about 0.4 moles of chromium, and from about 0.75 to about 1.25 moles of aluminum, per mole of phosphorous.
  • CAPO compositions may be prepared by using numerous reagents.
  • Reagents which may be employed to prepare CAPOs include:
  • TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
  • TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
  • CAPOs may be prepared by forming a starting reaction mixture by adding aluminum chlorhydrol or aluminum oxide to a solution of chromium acetate hydroxide in water, then adding successively phosphoric acid and the templating agent. Between each addition, and after formation of the final mixture, the mixture is blended until a homogeneous mixture is observed.
  • the phosphoric acid may be mixed with at least part of the water, and aluminum oxide or isopropoxide mixed in.
  • a solution of chromium acetate hydroxide is then added, followed by the templating agent, and the resultant mixture mixed until homogeneous.
  • amorphous chromium phosphate is ground dry with aluminum oxide and the resultant dry mixture added to an aqueous solution of phosphoric acid in an ice bath. The templating agent is then added, and the final mixture mixed until homogenous.
  • this mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
  • GaAPO MOLECULAR SIEVES The GaAPO molecular sieves of U.S. Serial No. 599,771, filed April 13, 1984, and U.S. Serial No. 830,890 filed February 19, 1986 have a framework structure of GaO 2 -, AlO 2 and PO 2 tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of "R” present per mole of (Ga x Al y P z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
  • x, "y” and “z” represent the mole fractions of the elements gallium, aluminum and phosphorous, respectively, present as tetrahedral oxides.
  • the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • the value ,of "z" in the GaAPO molecular sieves is not greater than about 0.60.
  • the values of x, y and z are within the limiting compositional values or points as follows:
  • the values of x, y and z are as follows:
  • GaAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of gallium, aluminum and phosphorous, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the GaAPO product are obtained, usually a period of from several hours to several weeks.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • reaction mixture composition expressed in terms of the molar ratios as follows:
  • R is an organic templating agent
  • a is the amount of organic templating agent “R” and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 1.0
  • "b” has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably between about 2 and 20
  • "x", "y” and “z” represent the mole fractions of gallium, aluminum and phosphorous, respectively, and each has a value of at least 0.01.
  • reaction mixture is selected such that the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • reaction mixtures are those containing from 0.2 to 0.5 mole of Ga 2 O 3 and from 0.3 to 1 mole of Al 2 O 3 for each mole of
  • GaAPO compositions may be prepared by using numerous reagents.
  • Reagents which may be employed to prepare GaAPOs include: (a) aluminum isopropoxide;
  • TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
  • TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
  • GaAPOs may be prepared by forming a starting reaction mixture by mixing the phosphoric acid with at least part of the water. To this solution the aluminum oxide or isopropoxide is added. This mixture is then blended until a homogenous mixture is observed. To this mixture the gallium sulfate or gallium hydroxide and the templating agent are successively added and the resulting mixture blended until a homogeneous mixture is observed.
  • the aluminum oxide may be mixed with a solution of the gallium sulfate or hydroxide, and then the phosphoric acid and the templating agent successively added. The resulting mixture is then blended until a homogeneous mixture is observed.
  • the templating agent may be dissolved in water, the gallium hydroxide or sulfate added with stirring, a solution of the phosphoric acid added, and finally the aluminum oxide mixed in. The resulting mixture is then blended until a homogeneous mixture is observed.
  • the mixture is then placed in .a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressures.
  • GeAPO MOLECULAR SIEVES The GeAPO molecular sieves of U.S. Serial No. 599,807, filed April 13, 1984, and U.S. Serial No. 841,753 filed March 20, 1986 have a framework structure of GeO 2 , AIO 2 - and PO 2 + tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula: mR : (Ge x Al y P z )O 2
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of "R” present per mole of (Ge ⁇ Al y P z )O 2 and has a value of zero to. about 0.3, but is preferably not greater than 0.2
  • x, "y” and “z” represent the mole fractions of the elements germanium, aluminum and phosphorous, respectively, present as tetrahedral oxides.
  • the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • the values of x, y and z are within the limiting compositional values or points as follows:
  • An especially preferred subclass of the GeAPO molecular sieves are those in which the value of "x" is not greater than about 0.13.
  • .GeAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of germanium, aluminum and phosphorous, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the GeAPO product are obtained, usually a period of from several hours to several weeks.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • reaction mixture composition expressed in terms of the molar ratios as follows: aR : (Ge x Al y P z )O 2 : bH 2 O
  • R is an organic templating agent
  • a is the amount of organic templating agent "R” and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 0.6
  • b has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably between about 10 and about 60
  • "x", "y” and “z” represent the mole fractions of germanium, aluminum and phosphorous, respectively, and each has a value of at least 0.01.
  • reaction mixture is selected such that the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • reaction mixtures are those containing from 0.2 to 0.4 mole of GeO 2 and from 0.75 to 1.25 mole of Al 2 O 3 for each mole of
  • GeAPO compositions may be prepared by using numerous reagents.
  • Reagents which may be employed to prepare GeAPOs include:
  • germanium tetrachloride, germanium ethoxide and germanium dioxide (d) germanium tetrachloride, germanium ethoxide and germanium dioxide;
  • TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
  • TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
  • germanium and aluminum may be advantageous, when synthesizing the GeAPO compositions, to first combine sources of germanium and aluminum, to form a mixed germanium/aluminum compound (this compound being typically a mixed oxide) and thereafter to combine this mixed compound with a source of phosphorous to form the final GeAPO composition.
  • a mixed germanium/aluminum compound this compound being typically a mixed oxide
  • Such mixed oxides may be prepared for example by hydrolyzing aqueous solutions containing germanium tetrachloride and aluminum chlorhydrol, or aluminum tri-sec-butoxide.
  • GeAPOs may be prepared by forming a starting reaction mixture by mixing the phosphoric acid with at least part of the water. To this solution is added the mixed germanium/aluminum oxide prepared as described above. This mixture is then blended until a homogeneous mixture is observed. To this mixture the templating agent is added and the resulting mixture blended until a homogeneous mixture is observed.
  • germanium ethoxide may be added to a solution of aluminum isopropoxide.
  • the resultant solution may optionally be dried to produce a mixed oxide.
  • To the mixed solution or dried oxide are added successively the phosphoric acid and the templating agent. The resulting mixture is then blended until a homogeneous mixture is observed.
  • a solution is formed by dissolving the phosphoric acid in water, adding aluminum oxide or isopropoxide and mixing thoroughly.
  • a solution containing the templating agent and germanium dioxide To the resultant mixture is added a solution containing the templating agent and germanium dioxide. The resulting mixture is then blended until a homogeneous mixture is observed.
  • the -mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
  • LiAPO MOLECULAR SIEVES The LiAPO molecular sieves of U.S. Serial No. 599,811, filed April 13, 1984, and U.S. Serial No. 834,921 filed February 28, 1986 have a framework structure of LiO 2 -3 , AlO 2 - and PO 2 + tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • m represents the molar amount of "R” present per mole of (Li x Al y P z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
  • x, "y” and “z” represent the mole fractions of the elements lithium, aluminum and phosphorous, respectively, present as tetrahedral oxides.
  • the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • the values of x, y and z are within the limiting compositional values or points as follows:
  • LiAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of lithium, aluminum and phosphorous, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
  • the reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the LiAPO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 12 hours to about 5 days, have been observed.
  • the product is recovered by any convenient method such as centrifugation or filtration.
  • reaction mixture composition expressed in terms of the molar ratios a's follows:
  • R is an organic templating agent
  • a is the amount of organic templating agent “R” and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 2
  • "b” has a value of from zero (0) to about 500, preferably between 2 and 300, most preferably not greater than about 40
  • "x", "y” and “z” represent the mole fractions of lithium, aluminum and phosphorous, respectively, and each has a value of at least 0.01.
  • reaction mixture is selected such that the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
  • LiAPO molecular sieves Since the exact nature of the LiAPO molecular sieves is not clearly understood at present, although all are believed to contain LiO, tetrahedra in the three-dimensional microporous crystal framework structure, it is advantageous to characterize the LiAPO molecular sieves by means of their chemical composition. This is due to the low level of lithium present in certain of the LiAPO molecular sieves prepared to date which makes it difficult to ascertain the exact nature of the interaction between lithium, aluminum and phosphorous. As a result, although it is believed that LiO 2 tetrahedra are substituted isomorphously for AIO 2 or PO 2 tetrahedra, it is appropriate to characterize certain LiAPO compositions by reference to their chemical composition in terms of the mole ratios of oxides. Molecular sieves containing lithium, aluminum and phosphorous as framework tetrahedral oxide units are prepared as followed:
  • LiAPO compositions may be prepared by using numerous reagents.
  • Reagents which may be employed to prepare LiAPOs include:
  • TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
  • TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
  • LiAPOs may be prepared by forming a starting reaction mixture by suspending aluminum oxide in at least part of the water. To this mixture the templating agent is added. The resultant mixture is then blended until a homogeneous mixture is observed. To this mixture the lithium phosphate or sulfate is added and the resulting mixture blended until a homogeneous mixture is observed.
  • an initial mixture may be formed by mixing aluminum oxide and lithium phosphate or sulfate.
  • To the resultant mixture are added successively phosphoric acid and an aqueous solution of the templating agent, and the resulting mixture blended until a homogeneous mixture is observed.
  • the phosphoric acid is mixed with at least part of the water, and the aluminum oxide is mixed in.
  • the resultant mixture are added lithium sulfate and the templating agent, and the resulting mixture blended until a homogeneous mixture is observed.
  • reaction mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
  • a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
  • FeTiAPO MOLECULAR SIEVES The FeTiAPO molecular sieves of U.S. Serial No. 599,824, filed April 13, 1984, and U.S. Serial No. 902,129 filed September 2, 1986 have three-dimensional microporous framework structures of FeO 2 n , TiO 2 , AlO 2 - and PO 2 + tetrahedral oxide units, where "n" is -2 or -1, and have an empirical chemical composition on an anhydrous basis expressed by the formula:
  • R represents at least one organic templating agent present in the intracrystalline pore system
  • M represents iron and titanium
  • m represents the molar amount of "R” present per mole of (M x Al y P z )O 2 and has a value of ze.ro (0) to about 0.3
  • x, "y” and ⁇ "z” represent the mole fractions of "M", aluminum and phosphorus, respectively present as tetrahedral oxides.
  • the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:

Abstract

Processes for preparing triethylenediamine and/or one or more cyclic or acyclic amines by contacting one or more amine starting materials with one or more molecular sieves. By proper choice of catalysts and/or reaction conditions, the processes of this invention can be varied to alter their selectivity to a number of differing and useful products, including triethylenediamine and substituted triethylenediamines.

Description

PROCESSES FOR THE PRODUCTION OF AMINES
This application is a cohtinuation-in-part of U.S. Patent Application Serial No. 134,815, filed December 18, 1987.
Related Applications U.S. Patent Application Serial No. 134,863, filed December 18, 1987, and U.S. Patent No. 134,815, filed December 18, 1987, both of which are commonly assigned.
Brief Summary of the Invention
Field of the Invention
This invention relates to processes for the production of amines. More specifically, this invention relates to processes for preparing triethylenediamine and/or one or more cyclic or acyclic amines by contacting one or more amine starting materials with one or more molecular sieves. By proper choice of catalysts and/or reaction conditions, the processes of this invention can be varied to alter their selectivity to a number of differing and useful products, including triethylenediamine and substituted triethylenediamines.
Background of the Invention
Triethylenediamine, also referred to as 1,4-diazabicyclo[2.2.2] octane or DABCO, is an item of commerce which is used as a catalyst for -OH + OCN- reactions to form the urethane linkage in polyurethanes. Various processes for the production of triethylenediamine are known. For example, triethylenediamine may be produced by the method disclosed in WO 87/03592, published June 18, 1987. As disclosed therein, triethylenediamine may be produced by bringing an amine compound having a specific amino group into contact with a crystalline metal silicate catalyst wherein the molar ratio of silicon dioxide (SiO2) to an oxide of a trivalent metal (M2O3:M being a trivalent metal) is 12 or more.
European Patent Application No. 0158319, published October 16, 1985, discloses a method for preparing 1,4-diazabicyclo[2.2.2]octanes by contacting acyclic or heterocyclic amines with a high-silica zeolite having a silica to alumina ratio of at least 20 to 1.
European Patent Application No. 0263463, published April 13, 1988, discloses a method for preparing 1,4-diazabicyclo[2.2.2]octane and C-substituted 1,4-diazabicyclo[2.2.2]octane by reacting a particular heterocyclic amine in the presence of L-zeolites, phosphates with zeolite structure and zirconium phosphates as catalysts.
The mixtures produced by these prior art processes can pose problems of separation. In addition, the relative proportions in which the various products are produced are rarely optimal with regard to the commercial demand for, and selling prices of, the various products, and thus it would be highly advantageous to be able to vary the product distribution to increase the proportions of the more valuable products produced. It has now been discovered that the product distribution obtained in the aforementioned reactions of amines can be improved by using as the catalyst in such reactions certain selected molecular sieves and/or by varying certain reaction conditions. Summary of the Invention
This invention relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting two or more amine starting materials with one or more molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves, the contacting of the two or more amine starting materials with the one or more molecular sieves being effected under conditions effective to convert at least one of the amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
This invention also relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more modified molecular sieves selected from (a) modified silica molecular sieves, (b) modified non-zeolitic molecular sieves, and (c) modified zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more modified molecular sieves being effected under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
This invention further relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more non-zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more non-zeolitic molecular sieves being effected under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
This invention yet further relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more molecular sieves being effected in the presence of water or steam and under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
Detailed Description As indicated above, this invention relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting two or more amine starting materials with one or more molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves, the contacting of the two or more amine starting materials with the one or more molecular sieves being effected under conditions effective to convert at least one of the amine starting, materials into triethylenediamine and/or one or more cyclic or acyclic amines.
As indicated above, this invention also relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more modified molecular sieves selected from (a) modified silica molecular sieves, (b) modified non-zeolitic molecular sieves, and (c) modified zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more modified molecular sieves being effected under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
As indicated above, this invention further relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more non-zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more non-zeolitic molecular sieves being effected under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
As indicated above, this invention yet further relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or mo-re amine starting materials with one or more molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more molecular sieves being effected in the presence of water or steam and under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
The processes of the present invention are useful for the production of various substituted and unsubstituted cyclic and acyclic amines. Illustrative cyclic and acyclic amines include, for example, triethylenediamine, substituted triethylenediamines, pyrazine, substituted pyraz.ines, pyridine, substituted pyridines, piperidine, substituted piperidines, piperazine, substituted piperazines, aminoethylethanolamine, diethanolamine, ethylendiamine, morpholine, substituted morpholines, alkyleneamines, alkanolamines, alkylamines, polyalkylene polyamines, allylamines and the like.
The processes of the present invention are useful for the conversion of piperazine to triethylenediamine and/or one or more of pyrazine, substituted pyrazines including methyl/ethyl substituted pyrazines, substituted piperazines including N-ethylpiperazine,
N-(2-hydroxyethyl) piperazine, N-(2-aminoethyl)- piperazine and N-formyl piperazine, aminoethylethanolamine, diethanolamine, ethylenediamine, substituted triethylenediamines, methylamine, ethylamine, acetonitrile and morpholine.
As indicated above, the products prepared by the processes of the present invention may include both acyclic and cyclic amines. The cyclic products may include both monocyclic materials, for example substituted piperazines, pyrazines and morpholines, and products containing more than one ring. For example, under certain conditions, when one or more of monoethanolamine, piperazine, ethylene glycol, N-(2-aminoethyl)piperazine, N-(2-hydroxyethyl)piperazine, ethylenediamine and other ethyleneamines and ethanolamines (or certain other starting materials) are subjected to the processes of the present invention, the products can selectively include triethylenediamine or 1,4-diazabicyclo[2.2.2]octane (DABCO). Also, under certain conditions, when one or more of piperazine, propylene glycol, isopropanolamine and other methylated ethyleneamines and methylated ethanolamines (or certain other starting materials) are subjected to the processes of the present invention, the products can selectively include a mixture of 2-methyl-triethylenediamine or 2-methyl-1,4-diazabicyclo[2.2.2] octane (methyl DABCO) and triethylenediamine or 1,4-diazabicyclo[2.2.2]octane (DABCO). Multiple methyl homologues of 2-methyl-triethylenediamine may also be produced by the processes of this invention. The preferred catalysts for the above conversions include Silicalite, a microporous form of silica described in U.S. Patent No. 4,061,724 issued December 6, 1977 to R.W. Grose et al., and Silicalite treated with phosphoric acid or phosphoric acid equivalents such as diammonium hydrogen phosphate as described hereinbelow.
Various amine and optionally non-amine starting materials can be used in the processes of this invention. Illustrative amine starting materials include one or more, substituted or unsubstituted, cyclic or acyclic amines such as piperazine, monoethanolamine, alkanolamines, ethylenediamine, propylenediamine, butylenediamine, alkylenediamines, isopropanσlamine, diisopropanolamine, alkylamines, substituted piperazines, N-(2-hydroxyethyl)piperazine, N-(2-aminoethyl)piperazine, diethanolamine, triethanolamine, substituted morphόlines, morpholine, diethylenetriamine, triethylenetetraamime, higher polyalkylene polyamines and the like. Illustrative non-amine starting materials which may be used in combination with amine starting materials include one or more diols such as ethylene glycol, propylene glycol and the like. A preferred embodiment of this invention involves co-feeding piperazine and ethylenediamine to selectively produce triethylenediamine at enhanced reaction rates. The molar ratio of amine and non-amine starting materials used in the processes of this invention can vary over a wide range. The preferred molar ratio of amine and non-amine starting material(s) depends not only on the product ratio desired but also on reaction conditions. Since the product ratio changes with changing conversion, the preferred molar ratio for any desired product mix will change with pressure or temperature or anything else that affects the conversion.
Suitable molecular sieves for use in this invention include, for example, the silica molecular sieves, such as Silicalite (U.S. Patent No. 4,061,724), Silicalite II (D. M. Bibby, et al.. Nature, 1979, Vol. 280, pg. 664), and fluoride Silicalite (U.S. Patent No. 4,073,865).
Other suitable molecular sieves for use in this invention include the non-zeolitic molecular sieves having an empirical chemical composition on an anhydrous basis expressed by the formula:
(I) mR: (QwAlχPySiz)O2
where "Q" represents at least one element present as a framework oxide unit "QO2 n" with charge "n" where "n" may be -3, -2, -1, 0 or +1; "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of
(QwAlxPySiz)O2 and has a value from zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of QO2 n, AlPO2-, PO2 +, SiO2, respectively, present as framework oxide units. "Q" is characterized as an element having a mean "T-O" distance in tetrahedral oxide structures between about 1.51 Angstroms and about 2.06 Angstroms. "Q" has a cation electronegativity between about 125 kcal/gm-atom to about 310 kcal/gm-atom and "Q" is capable of forming stable Q-O-P, Q-O-Al or Q-O-Q bonds in crystalline three dimensional oxide structures having a "Q-O" bond dissociation energy greater than about 59 kcal/gm-atom at 298°K; and said mole fractions being within the limiting compositional values or points as follows: w is equal to 0 to 98 mole percent; y is equal to 1 to 99 mole percent; x is equal to 1 to 99 mole percent; and z is equal to 0 to 98 mole percent.
The "Q" of. the "QAPSO" molecular sieves of formula (I) may be defined as representing at least one element capable of forming a framework tetrahedral oxide and may be one of the elements arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium and zinc. The invention contemplates combinations of the elements as representing Q, and to the extent such combinations are present in the structure of a QAPSO they may be present- in molar fractions of the Q component in the range of 1 to 99 percent thereof. It should be noted that Formula (I) contemplates the non-existence of Q and Si. In such case, the operative structure is that of AlPO4 as discussed below. Where z has a positive value, then the operative structure is that of SAPO, discussed below. Thus, the term QAPSO does not perforce represent that the elements Q and S (actually Si) are present. When Q is a multiplicity of elements, then to the extent the elements present are as herein contemplated, the operative structure is that of the ELAPSO or ELAPO or MeAPO or MeAPSO molecular sieves, as herein discussed. However, in the contemplation that molecular sieves of the QAPSO variety will be invented in which Q will be another element or elements, then it is the intention to embrace the same as a suitable molecular sieve for the practice of this invention.
Illustrations of QAPSO compositions and structures are the various non-zeolitic compositions and structures described hereinbelow.
Still other suitable molecular sieves for use in this invention include zeolitic molecular. sieves such as chabazite, faujasite, levynite, Linde Type A, gismondine, erionite, sodalite, Linde Type X and Y, analcime, gmelinite, harmontome, mordenite, epistilbite, heulandite, stilbite, edingtonite, mesolite, natrolite, scolecite, thomsonite, brewsterite, laumontite, phillipsite, ZSM-5 (U.S. Patent No. 3,702,886), ZSM-20 (U.S. Patent No. 3,972,983), ZSM-11 (U.S. Patent No. 3,709,979), ZSM-12 (U.S. Patent No. 3,832,449), ZSM-34 (U.S. Patent No. 4,086,186), LZ-105 (U.S. Patent No. 4,257,885) and Beta (U.S. Patent No. 3,308,069 and U.S. Reissue Patent No. 28,341), and the like. Typical of suitable zeolitic molecular sieves employable in the practice of this invention are those reviewed by Flanigen in Pure & Applied Chemistry, Vol. 52. pp. 2191-2211, 1980, including their ion exchanged forms. Zeolite ion exchange is reviewed by D. W. Breck in Chapter 7 of his book, "Zeolite Molecular Sieves", Wiley-Interscience, New York 1974. Also suitable are the zeolitic molecular sieves discovered since these reviews such as: LZ-210, LZ-211, LZ-212, etc. all from U.S. Patent 4,503,023, EU-13, U.S. -Patent 4,581,211, ISI-6, U.S. Patent 4,578,529, and the like including their ion exchanged forms.
Preferred molecular sieves for use in this invention have a crystalline structure related to the pentasil type. Silica molecular sieves, e.g., Silicalite, and zeolitic molecular sieves, e.g., Z5M-5, are particulary desirable for use in this invention. Preferred molecular sieves for use in this invention may have a silicon: aluminum ratio of at least about 6:1, preferably 10:1 or 20:1, and more preferably 40:1 or 60:1 or even greater. Aluminum may be a desired component of the molecular sieves even at very low concentrations. Aluminum present as framework aluminum may be more desirable than non-framework aluminum.
In their as-synthesized form, the molecular sieves typically contain within their internal pore systems at least one form of the organic templating agents used in their synthesis. Most commonly the organic moiety is present, at least in part, as a charge-balancing cation, and indeed this is generally the case with as-synthesized molecular sieves prepared from organic-containing reaction systems. It is possible, however, that some or all of the organic moiety is an occluded molecular species in a particular species of molecular sieve. As a general rule the templating agent, and hence the occluded organic species, is too large to move freely through the pore system of the molecular sieve and must be removed by calcining the molecular sieve in air at temperatures of 200° to 700°C, preferably about 350° to about 600°C, to thermally degrade the organic species. In a few instances the pores of the molecular sieve are sufficiently large to permit transport of the templating agent, particularly if the latter is a small molecule, and accordingly complete or partial removal thereof can be accomplished by conventional desorption procedures, such as hydrotreating or chemical treatment such as solvent extraction, which will be familiar to those skilled in the molecular sieve art. In some cases, the organic templating agent may be removed in situ by placing the molecular sieve still containing the organic templating agent in the reactor, so that the organic templating agent is removed under reaction conditions.
The molecular sieves used in this invention offer an inherent limitation to the transformation of amine starting materials to various amine products. In order to react within the molecular sieve catalyst, the amine molecule should have (i) a kinetic diameter which is less than the limiting aperture of the molecular sieve pore in order to enter the catalyst or (ii) a transition state during the reaction which is not larger than the molecular sieve pore or cavity in order transform in the catalyst. The resulting amine products should have a kinetic diameter less than the limiting aperture of the molecular sieve pore in order to exit the catalyst.
The term "non-zeolitic molecular sieves" or "NZMS" is defined in the instant invention to include the "SAPO" molecular sieves of U.S. Patent No. 4,440,871 and U.S.. Serial No. 575,745, filed January 31, 1984, "ELAPSO" molecular sieves as disclosed in U.S. Serial No. 600,312, filed April 13, 1984, and certain "AlPO4", "MeAPO", "FeAPO", "TAPO" and "ELAPO" molecular sieves, as hereinafter described. Crystalline "AlPO4" aluminophosphates are disclosed in U.S. Patent No. 4,310,440 issued January 12, 1982, and in U.S. Serial No. 880,559, filed June 30, 1986; crystalline metal aluminophosphates (MeAPOs where "Me" is Mg, Mn, Co and Zn) are disclosed in U.S. Patent No. 4,567,029, issued January 28, 1986; crystalline ferroaluminophosphates (FeAPOs) are disclosed in U.S. Patent No. 4,554,143, issued November 19, 1985; titanium aluminophosphates (TAPOs) are disclosed in U.S. Patent No. 4,500,651, issued February 19, 1985; certain non-zeolitic molecular sieves ("ELAPO") are disclosed in EPC Patent Application 85104386.9 (Publication No. 0158976, published October 13, 1985) and 85104388.5 (Publication No. 158349, published October 16, 1985); and ELAPSO molecular sieves are disclosed in copending U.S. Serial No. 600,312, filed April 13, 1984 (EPC Publication No. 0159624, published October 30, 1985). The aforementioned applications and patents are incorporated herein by reference thereto. The nomenclature employed herein to refer to the members of the aforementioned NZMSs is consistent with that employed in the aforementioned applications or patents. A particular member of a class is generally referred to as a "-n" species wherein "n" is an. integer, e.g., SAPO-11, MeAPO-11 and ELAPSO-31. In the- following discussion on NZMSs set forth hereinafter the mole fraction of the NZMSs are defined as compositional values which are plotted in phase diagrams in each of the identified patents, published applications or copending applications.
ELAPSO MOLECULAR SIEVES "ELAPSO" molecular sieves are described in copending U.S. Serial No. 600,312, filed April 13, 1984, (EPC Publication No. 0159,624, published October 30, 1985, incorporated herein by reference) as crystalline molecular sieves having three-dimensional microporous framework structures of ELO2, AlPO2, PO2, SiO2 oxide units and having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (ELwAlxPySiz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (ELwAlxPySiz)O2 and has a value of from zero to about 0.3; "EL" represents at least one element capable of forming a three dimensional oxide framework, "EL" being characterized as an element having a mean "T-O" distance in tetrahedral oxide structures between about 1.51 Angstroms and about 2.06 Angstroms, "EL" having a cation electronegativity between about 125 Kcal/g-atom to about 310 Kcaϊ/gm-atom and "EL" being capable of forming stable M-O-P, M-O-Al or M-O-M bonds in crystalline three dimensional oxide structures having a "M-O" bond dissociation energy greater than about 59 kcal/g-atom at 298°K; and "w", "x", "y" and "z" represent the mole fractions of "EL", aluminum, phosphorus and silicon, respectively, present as framework oxides, said mole fractions being within the limiting compositional values or points as follows:
Mole Fraction
Point X y (z + w)
A 0 . 60 0 .39-(0 .01) ρ 0 .01 (p + 1)
B 0.39-(0 .01p) 0. 60 0 .01 (p + 1)
C 0. 01 0. 60 0 .39
D 0 .01 0.01 0 . 98
E 0 . 60 0 .01 0 .39
where "p" is an integer corresponding to the number of elements "El" in the (ElwAlxPySiz)O2 constituent.
The "ELAPSO" molecular sieves are also described as crystalline molecular sieves having three-dimensional microporous framework structures of ELO2, AlPO2, SiO2 and PO2 tetrahedral oxide units and having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (ELwAlxPySiz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (ELwAlxPySiz)O2 and has a value of from zero to about 0.3; "EL" represents at least one element capable of forming a framework tetrahedral oxide and is selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium and zinc; and "w", "x", "y" and "z" represent the mole fractions of "EL", aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being within the limiting compositional values or points as follows:
Mole Fraction
Point X V (z + w) a 0.60 0.39-(0.01)p 0.01(p + 1) b 0.39-(0.01p) 0.60 0.01(p + 1) c 0.10 0.55 0.35 d 0.55 0.10 0.35
where "p" is as above defined. The "ELAPSO" molecular sieves include numerous species which are intended herein to be within the* scope of the term "non-zeolitic molecular sieves" such being disclosed in the following copending and commonly assigned applications, incorporated herein by reference thereto [(A) following a serial number indicates that the application is abandoned, while (CIP) following .a serial number indicates that the application is a continuation-in-part of the immediately preceding application and (C) indicates that the application is a continuation of the immediately preceding application]: U.S. Serial No. Filed NZMS
599, 808(A) April 13, 1984 AsAPSO
845,484(CIP) March 31, 1986 AsAPSO
600,177(A) April 13, 1984 BAPSO
845,255(CIP) March 28, 1986 BAPSO
600,176(A) April 13, 1984 BeAPSQ
841,752(CIP) March 20, 1986 BeAPSO
599,830(A) April 13, 1984 CAPSO
852,174(CIP) April 15, 1986 CAPSO
599,925(A) April 13, 1984 GaAPSO
845,985(CIP) March 31, 1986 GaAPSO
599,971(A) April 13, 1984 GeAPSO
852,175(CIP) April 15, 1986 GeAPSO
599,952(A) April 13, 1984 LiAPSO
847,227(CIP) April 2, 1986 LiAPSO
600,179 April 13, 1984 TiAPSO
(now U.S. Patent 4,684,617 issued August 4, 1987)
049,274(C) May 13, 1987 TiAPSO
600,180 April 13, 1984 MgAPSO U.S. Serial No. Filed NZMS
600,175 April 13, 1984 MnAPSO
(now U.S. Patent 4,686,092 issued August 11, 1987)
600,174 April 13, 1984 CoAPSO
600,170 April 13, 1984 ZnAPSO
600,173 April 13, 1984 FeAPSO
(now U.S. Patent 4,683,217 issued July 28, 1987)
600, 168 (A) April 13, 1984 QuinAPSO
063, 791(C) June 22, 1987 QuinAPSO
600.181 April 13, 1984 QuinAPSO
600.182 April 13, 1984 CoMnMgAPSO 057,648(C) June 9, 1987 CoMnMgAPSO
600.183 April 13, 1984 SenAPSO
The disclosures of the patents listed in the foregoing table are herein incorporated by reference.
TiAPSO MOLECULAR SIEVES
As already mentioned, the TiAPSO molecular sieves are described in U.S. Patent No. 4,684,617 (incorporated herein by reference); these TiAPSO molecular sieves are also described in U.S. Serial No. 049,274, filed May 13, 1987.
MqAPSO MOLECULAR SIEVES The MgAPSO molecular sieves of U.S. Serial No. 600,180, filed April 13, 1984 have three-dimensional microporous framework structures of MgO2 -2, AlO2-, PO2 + and SiO2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula: mR : (MgwAlxPySiz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (MgwAlxPySiz)O2 and has a value from zero (0) to about 0.3; and "w", "x", "y" and "z" represent the. mole fractions of magnesium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides and each preferably has a value of at least 0.01. The mole fractions "w", "x", "y" and " z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point X y (z + w)
A 0.60 0.38 0.02
B 0.39 0.59 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of the MgAPSO molecular sieves the values "w", "X", "y" and "z" in the above formula are within the limiting compositional values or points as follows:
Mole Fraction
Point X Y (z + w) a 0.55 0.43 0.02 b 0.43 0.55 0.02 c 0 . 10 0 . 55 0 . 35 d 0 . 55 0 . 10 0 . 35
MgAPSO compositions are generally synthesized by hydrothermal crystallization for an effective time at effective pressures and temperatures from a reaction mixture containing reactive sources, of magnesium, silicon, aluminum and phosphorus, an organic templating, i.e., structure-directing, agent, preferably a compound of an. element of Group VA of the Periodic Table, and may be an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between 50°C and 250°C, and preferably between 100°C and 200°C until crystals of the MgAPSO product are obtained, usually a period of from several hours to several weeks. Generally, the crystallization period will be from about 2 hours to about 30 days with it typically being from about 4 hours to about 20 days for obtaining MgAPSO crystals. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the MgAPSO compositions, it is preferred to employ reaction mixture compositions expressed in terms of the molar ratios as follows:
aR : (MgwAlxP Siz)O2 : bH2O wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and can have a value within the range of from zero (0) to about 6 and is more preferably an effective amount greater than zero to about 6; "b" has a value of from zero (0) to about 500, preferably between about
2 and about 300; and "w", "x", "y" and "z" represent the mole fractions of magnesium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
In one embodiment the reaction mixture is selected such that the mole fractions "w", "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
F 0.60 0.38 0.02
G 0.38. 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "w", "x", "y" and "z" such that (w + x + y + z) = 1.00 mole. Molecular sieves containing magnesium, aluminum, phosphorus and silicon as framework tetrahedral oxides are prepared as follows: Preparative Reagents MgAPSO compositions are prepared using numerous reagents. Typical reagents which may be employed to prepare MgAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea for hydrated pseudoboehmite;
(c) LUDOX-LS: Trademark of DuPont for an aqueous solution of 30 weight percent SiO2 and 0.1 weight percent Na2O;
(d) Mg(Ac)2: magnesium acetate tetrahydrate, Mg(C2H3O2·4H2O;
(e) H3PO4: 85 weight percent aqueous phosphoric acid in water;
(f) TBAOH: tetrabutylammonium hydroxide (40 wt. % in water); (g) Pr2NH: di-n-propylamine; (h) Pr3NH: tri-n-propylamine; (i) Quin: Quinuclidine; (j) MQuin: Methyl Quinuclidine hydroxide,
(17.9%) in water); (k) C-hex: cyclohexylamine; (l) TEAOH: tetraethylammonium hydroxide
(40 wt. % in water); (m) DEEA: Diethylethanolamine; (n) i-Pr2NH: di-isopropylamine; (o) TEABr: tetraethylammonium bromide; and (p) TPAOH: tetrapropylammonium hydroxide
(40 wt . % in water).
Preparative Procedures The MgAPSO compositions may be prepared by preparing reaction mixtures having a molar composition expressed as: eR: fMgO :hAl2O3 : iP2O5 : gSiO2 : JH2O wherein e, f, g, h, i and j represent the moles of template R, magnesium (expressed as the oxide), SiO2, Al2O3, P2O5 (H3PO4 expressed as P2O5) and H2O, respectively;
The reaction mixtures may be prepared by the following representative procedures, designated hereinafter as Methods A, B and C.
Method A
The reaction mixture is prepared by mixing the ground aluminum source (alipro or CATAPAL) with the H3PO4 and water on a gradual basis with occasional cooling with an ice bath . The resulting mixture is blended until a homogeneous mixture is observed. When the aluminum source is CATAPAL the water and H3PO4 are first mixed with the CATAPAL added thereto. The magnesium acetate is dissolved in a portion of the water and is then added followed by addition of the LUDOX-LS. The combined mixture is blended until a homogeneous mixture is observed. The organic templating agent is added to this mixture and blended until a homogeneous mixture is observed. The resulting mixture (final reaction mixture) is placed in a lined (polytetrafluoro- ethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for an effective time. Alternatively, if the digestion temperature is 100°C the final reaction mixture is placed in a lined (polytetrafluoroethylene) screw top bottle for a time. Digestions are typically carried out under autogenous pressure. The products are removed from the reaction vessel, cooled and evaluated as set forth hereinafter.
Method B When method B is employed the organic templating agent is di-n-propylamine. The aluminum source, silicon source and one-half of the water are first mixed and blended until a homogeneous mixture is observed. A second solution was prepared by mixing the remaining water, the H3PO4. and the magnesium acetate. This solution is then added to the above mixture. The magnesium acetate and
H3PO4 solution is then added to the above mixture and blended until a homogeneous mixture is observed. The organic templating agent(s) is/are then added and the resulting reaction mixture digested and product recovered as in Method A.
Method C
Method C is carried out by mixing aluminum isopropoxide, LUDOX LS and water in a blender or by mixing water and aluminum iso-propoxide in a blender followed by addition of the LUDOX LS. H3PO4 and magnesium acetate are then added to the resulting mixture. The organic templating agent is then added to the resulting mixture and digested and product recovered as in Method A.
MnAPSO MOLECULAR SIEVES As already mentioned, the MnAPSO molecular sieves are described in U.S. Patent No. 4,686,092 issued August 11, 1987 (incorporated herein by reference). CoAPSO MOLECULAR SIEVES The CoAPSO molecular sieves of U.S. Serial No. 600,174, filed April 13, 1984 have three-dimensional microporous framework structures of CoO2 -2, AKO2-, PO2 + and SiO2 tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (Co2AlxPySiz)O2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (CowAlxPySiz)O2 and has a value of from zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of cobalt, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, where the mole fractions "w", "x", "y" and "z" are each at least 0.01 and are generally defined, as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39 In a preferred subclass of the CoAPSO molecular sieves the values of "w", "x", "y" and "z" in the above formula are within the limiting compositional values or points as follows:
Mole Fraction
Point x V (z + w) a 0 . 55 0 . 43 0 . 02 b 0 . 43 0 . 55 0 . 02 c 0 . 10 0 . 55 0 . 35 d 0 . 55 0 . 10 0 . 35
CoAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of cobalt, silicon, aluminum and phosphorus, an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and optionally an alkali metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at an effective temperature which is generally between 50°C and 250°C and preferably between 100°C and 200°C until crystals of the CoAPSO product are obtained, usually for an effective time of from several hours to several weeks. Generally the effective crystallization time will be from about 2 hours to about 30 days and typically from about 4 hours to about 20 days. The product is recovered by any convenient method such as centrifugation or filtration. In synthesizing the CoAPSO, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (CowAlxPySiz)O2 : bH 2O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6; "b" has a value of from zero (0) to about 500, preferably between about 2 and 300; and "w", "x", "y" and "z" represent the mole fractions of cobalt, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01. In a preferred embodiment the reaction mixture is selected such that the mole fractions "w", "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "w", "x", "y" and "z" such that (w + x + y + z) = 1.00 mole. Molecular sieves containing cobalt, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents CoAPSO compositions may be prepared using numerous reagents. Reagents which may be employed to prepare CoAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea Corporation for pseudoboehmite;
(c) LUDOX-LS: Trademark of DuPont for an aqueous solution of 30 weight percent SiO2 and 0.1 weight percent Na2O;
(d) Co(Ac)2: cobalt acetate, Co(C2H3O2)2.4H2O;
(e) CoSO4: cobalt sulfate, (CoSO4·7H2O);
(f) H3PO4: 85 weight percent phosphoric acid in water;
(g) TBAOH: tetrabutylammonium hydroxide (25 wt % in methanol);
(h) Pr2NH: di-n-propylamine,
(C3H7)2NH; (i) Pr3N: tri-n-propylamine,
(C3H7)3N; (j) Quin: Quinuclidine (C7H13N); (k) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH) : (l) C-hex: cyclohexylamine; (m) TEAOH: tetraethylammonium hydroxide
(40 wt. % in water) (n) DEEA: diethanolamine;
(o) TPAOH: tetrapropylammonium hydroxide
(40 wt. % in water); and (p) TMAOH: tetramethylammonium hydroxide
(40 wt. % in water).
Preparative Procedure CoAPSO compositions may be prepared by preparing reaction mixtures having a molar composition expressed as:
eR: fCoO: hAl2O3 : iP2O5 : gSiO2 : jH2O
wherein e, f, h, i, g and j represent the moles of template R, cobalt (expressed as the oxide), Al2O3, P2O5 (H3PO4 expressed as P2O5), SiO2 and H2O, respectively.
The reaction mixtures are prepared by forming a starting reaction mixture comprising the H3PO4 and one half of the water. This mixture is stirred and the aluminum source (Alipro or CATAPAL) added. The resulting mixture is blended until a homogeneous mixture is observed. The LUDOX-LS is then added to the resulting mixture and the new mixture blended until a homogeneous mixture is observed. The cobalt source (e.g., Co(Ac)2, Co(SO4) or mixtures thereof) is dissolved in the remaining water and combined with the first mixture. The combined mixture is blended until a homogeneous mixture is observed. The organic templating agent is added to this mixture and blended for about two to four minutes until a homogeneous mixture is observed. The resulting mixture (final reaction mixture) is placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C, 200°C or 225°C) for a time. Digestions are typically carried out at the autogenous pressure. The products are removed from the reaction vessel and cooled.
ZnAPSO MOLECULAR SIEVES The ZnAPSO molecular sieves of U.S. Serial No. 600,170, filed April 13, 1984 comprise framework structures of ZnO2 -2, AlO2-, PO2 + and SiO2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (ZnwAlχPySiz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (ZnwAlxPySiz)O2 and has a value of zero to about 0.3; and "w", "x", "y" and " z" represent the mole fractions of zinc, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides and each has a value of at least 0.01. The mole fractions "w", "x", "y" and "z" are generally defined being within the limiting compositional values or points as follows: Mole Fraction
Point X y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0..01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of ZnAPSO molecular sieves the values "w", "x", "y" and "z" in the above formula are within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
a 0.55 0.43 0.02 b 0.43 0.55 0.02 c 0.10 0.55 0.35 d 0.55 0.10 0.35
ZnAPSO compositions are generally synthesized by hydrothermal crystallization at effective process conditions from a reaction mixture containing active sources of zinc, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element or Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure, at a temperature between 50°C and 250°C, and preferably between 100°C and 200°C until crystals of the ZnAPSO product are obtained, usually a period of from several hours to several weeks. Generally the effective crystallization period is from about 2 hours to about 30 days with typical periods of from about 4 hours to about 20 days being employed to obtain ZnAPSO products. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the ZnAPSO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (ZnwAlxPySiz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero, to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6; "b" has a value of from zero (0) to about 500, more preferably between about 2 and about 300; and "w", "x", "y" and "z" represent the mole fractions of zinc, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01. In a preferred embodiment the reaction mixture is selected such that the mole fractions "w", "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "w", "x", "y" and "z" such that (w + x + y + z) = 1.00 mole. Molecular sieves containing zinc, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents ZnAPSO compositions are typically prepared using numerous reagents. Reagents, which may be employed to prepare ZnAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) LUDOX-LS: LUDOX-LS is the trade name of DuPont for an aqueous solution of 30 weight percent SiO2 and 0.1 weight percent Na2O;
(c) CATAPAL: Trademark of Condea Corporation for hydrated pseudoboehmite; (d) H3PO4: 85 weight percent aqueous phosphoric acid;
(e) ZnAc: Zinc Acetate, Zn(C2H3O2)2·4H2O;
(f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(h) TMAOH: Tetramethylammonium hydroxide pentahydrate, (CH3)4N0H·5H2O; (i) TPAOH: 40 weight percent aqueous solution of tetrapropylammonium hydroxide, (C3H7)4NOH; (j) Pr2NH: Di-n-propylamine,
(C3H7)2NH; (k) Pr3N: Tri-n-propylamine,
(C3H7)3N; (l) Quin: Quinuclidine, (C7H13N) ; (m) C-hex: cyclohexylamine; and (n) DEEA: diethylethanolamine,
(C2H5)2NC2H5OH.
Preparative Procedure ZnAPSO compositions are typically prepared by forming reaction mixtures having a molar composition expressed as:
eR: fZnO:gAl2O3 : hP2O5 : iSiO2 : JH2O
wherein e, f, g, h, i and j represent the moles of template R, zinc (expressed as the oxide), Al2O3, P2O5 (H3PO4 expressed as P2O5), SiO2 and H2O, respectively.
The reaction mixtures are generally prepared by forming a starting reaction mixture comprising the H3PO4 and a portion of the water. This mixture is stirred and the aluminum source added. The resulting mixture is blended until a homogeneous mixture is observed. The LUDOX LS is then added to the resulting mixture and the new mixture blended until a homogeneous mixture is observed. The zinc source (zinc acetate) is dissolved in the remaining water and combined with the first mixture. The combined mixture is blended until a homogeneous mixture is observed. The organic templating agent is added to this mixture and blended for about two to four minutes until a homogeneous mixture is observed. The resulting mixture (final reaction mixture) is placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at an effective temperature for an effective time. Digestions are typically carried out under autogenous pressure. The products are removed from the reaction vessel and cooled.
FeAPSO MOLECULAR SIEVES
As already mentioned, the FeAPSO molecular sieves are described in U.S. Patent No. 4,683,217 (incorporated herein by reference).
QUINARY MOLECULAR SIEVES The QuinAPSO quinary molecular sieves of U.S. Serial Nos. 600,168 and 600,181, both filed
April 13, 1984, have three-dimensional microporous framework structures of MO2 n, AlO2-,
PO2 + and SiO2 tetrahedral units, where "n" is
-3, -2, -1, 0 or +1, and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (MwAlxPySiz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (MwAlχPySiz)O2 and has a value of from zero (0) to about 0.3; M represents at least two elements selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium and zinc; and "w", "x", "y" and "z" represent the mole fractions of M, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. Preferably, M represents the combination of cobalt and manganese. The mole fractions "w", "x", "y", and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
A 0.60 0.37 0.03
B 0.37 0.60 0.03
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39 Preferably the mole fractions w, x, y and z will fall within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w) a 0.60 0.37 0.03 b 0.37 0.60 0.03 c 0.01 0.60 0.39 d 0.01 0.39 0.60 e 0.39 0.01 0.60 f 0.60 0.01 0.39
QuinAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of the elements M, aluminum, phosphorus and silicon and preferably an organic templating agent, i.e., structure-directing, agent. The structure-directing agents are preferably a compound of an element of Group VA of the Periodic Table, and may be an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure and at typical effective temperatures between 50°C and 250°C, preferably between 100°C and 200°C, until crystals of the QuinAPSO product are obtained, usually over a period of from several hours to several weeks. Typical effective crystallization times are from about 2 hours to 30 days with from about 4 hours to about 20 days being generally employed to obtain QuinAPSO products. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the QuinAPSO .compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (MwAlxPySiz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300; and "w", "x", "y" and "z" represent the mole fractions of elements M, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
In one embodiment the reaction mixture is selected such that the mole fractions "w", "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
F 0.60 0.37 0.03
G 0.37 0.60 0.03
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39 In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "w", "x" , "y" and "z" such that (w + x + y + z) = 1.00 mole. QuinAPSO compositions were prepared using numerous regents; the appropriate sources of the various elements M are the same as those used in the preparation of the various APO and APSO molecular sieves containing the same elements, as described in detail above and below.
Reagents which may be employed to prepare QuinAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO2 and 0.1 weight percent of Na2O;
(c) H3PO4: 85 weight percent phosphoric acid;
(d) MnAc: Manganese acetate, Mn(C2H3O2)2·4H2O (for QuinAPSOs containing manganese);
(e) CoAc: Cobalt Acetate, Co(C2H3O2)2·4H2O (for QuinAPSOs containing cobalt);
(f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide; and
(g) Pr2NH: di-n-propylamine, (C3H7)2NH. Preparative Procedures QuinAPSOs may be prepared by forming a starting reaction mixture by adding H3PO4 and one half of the quantity of water. To this mixture an aluminum isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture a silica (e.g., LUDOX-LS) is added and the .resulting mixture blended (about 2 minutes) until a homogeneous mixture is observed. A second mixture is prepared using manganese acetate (or a appropriate source of another element M) and one half of the remaining water. A third mixture is prepared using cobalt acetate (or a appropriate source of another element M) and one half of the remaining water. The three mixtures are admixed and the resulting mixture blended until a homogeneous mixture is observed. The organic templating agent is then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture is observed, i.e., about 2 to 4 minutes. The pH of the mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at an effective temperature for an effective time. Digestions are typically carried out under autogeneous pressure.
CoMnMgAPSO MOLECULAR SIEVES The CoMnMgAPSO senary molecular sieves of U.S. Serial No. 600,182, filed April 13, 1984, and of U.S. Serial No. 057,648 filed June 9, 1987, have three-dimensional microporous framework structures of CoO2 -2, MnO2 -2, MgO2 -2, AlO2 , PO2 and SiO2 tetrahedral oxide units having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (CotMnuMgvAlxPySiz)O2
wherein "R" represents at least one organic templating agent .present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (CotMnuMgvAlxPySiz)O2 and has a value of from zero (0) to about 0.3; "t", "u", "v", "x", "y" and "z" represent the mole fractions of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides and each has a value of at least 0.01. The mole fractions "w, "x", "y" and "z", where "w" is the sum of "t" + "u" + "v", are. generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
A 0.60 0.36 0.04
B 0.36 0.60 0.04
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of the CoMnMgAPSO molecular sieves the values of "w", "x", "y" and "z" in the above formula are within the limiting compositional values or points as follows Mole Fraction
Point x y (z + w)
a 0 . 55 0 . 41 0 . 04 b 0 . 41 0 . 55 0 . 04 c 0 . 10 0 . 55 0 . 35 d 0 . 55 0 . 10 0 . 35
CoMnMgAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, and preferably an organic templating agent, i.e., structure-directing agent. The structure-directing agents are preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between 50°C and 250°C, and preferably between 100°C and 200°C, until crystals of the CoMnMgAPSO product are obtained, usually over a period of from several hours to several weeks. Typical crystallization times are from about 2 hours to about 30 days with from about 4 hours to about 20 days generally being employed to obtain CoMnMgAPSO products. The product is recovered by any convenient method such as centrifugation or filtration. In synthesizing the CoMnMgAPSO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (CotMnuMgvAlxPySiz)O2 : bH2O wherein "R" is an organic templating agent; "a" is the amount of org'anic templating agent "R" and has a value, of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6 and more preferably from greater than zero to about 2; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300; and "t", "u", "v", "x", "y", and "z" represent the mole fractions of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
In a preferred embodiment the reaction mixture is selected such that the mole fractions "w", "x", "y" and "z", where "w" is the sum of "t" + "u" + "v", are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
F 0.60 0.36 0.04
G 0.36 0.60 0.04
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39 In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "t", "u", "v", "x", "y" and "z" such that (t + u + v + x + y + z) = 1.00 mole. Molecular sieves containing cobalt, manganese, magnesium, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents CoMnMgAPSO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare CoMnMgAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO2 and 0.1 weight percent Na2O;
(c) H3PO4: aqueous solution which is 85 weight percent phosphoric acid;
(d) MnAc: Manganese acetate, Mn(C2H3O2)2·4H2O;
(e) CoAc: Cobalt Acetate; Co(C2H3O2)2·4H2O;
(f) MgAc: Magnesium Acetate Mg(C2H3O2)·4H2O;
(g) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide; and
(h) Pr2NH: di-n-propylamine, (C3H7)2NH. Preparative Procedures CoMnMgAPSOs may be prepared by forming a starting reaction mixture by adding H3PO4 and one half of the quantity of water. To this mixture an aluminum isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture a silica (e.g., LUDOX-LS) is added and the resulting mixture blended (about 2 minutes) until a homogeneous mixture is observed.
Three additional mixtures are prepared using cobalt acetate, magnesium acetate and manganese acetate using one third of the remainder of the water for each mixture. The four mixtures are then admixed and the resulting mixture blended until a homogeneous mixture is observed. An organic templating agent is then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture is observed, i.e., about 2 to 4 minutes. The mixture is then placed in a lined . (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature for a time. Digestions are typically carried out under autogenous pressure.
SenAPSO MOLECULAR SIEVES The SenAPSO molecular sieves of U.S. Serial No. 600,183, filed April 13, 1984 have three-dimensional microporous framework structures of MO2 n, AlO2-, PO2 + and SiO2 tetrahedral oxide units, where "n" is -3, -2, -1, 0 or +1, and have an empirical chemical composition on an anhydrous basis expressed by the formula: mR : (MwAlχPySiz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (MwAlxPySiz)O2, and has a value of from zero to about 0.3; "M" represents three elements selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium and zinc; "n" may have the aforementioned values depending upon the oxidation state of "M" ; and "w", "x", "y" and "z" represent the mole fractions of elements "M", aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. The mole fractions "w", "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows, wherein "w" denotes the combined mole fractions of the three elements "M" such that "w" =
"w1" + "w2" + "w3" and each element "M" has a mole fraction of at least 0.01:
Mole Fraction
Point x . y (z + w)
A 0.60 0.36 0.04
B 0.36 0.60 0.04
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39 In a preferred subclass of the SenAPSO molecular sieves the values of "w", "x", "y" in the above formula are within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w) a 0.60 0.36 0.04 b 0.36 0.60 0.04 c 0.01 0.60 0.39 d 0.01 0.39 0.60 e 0.39 0.01 0.60 f 0.60 0.01 0.39
SenAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of elements "M", aluminum, phosphorus and silicon, and preferably an organic templating, i.e., structure-directing, agent. The structure-directing agents are preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between 50°C and 250°C, and preferably between 100°C and 200°C, until crystals of the SenAPSO product are obtained, usually over a period of from several hours to several weeks. Typical crystallization times are from about 2 hours to about 30 days with from about 4 hours to about 20 days generally being employed to obtain SenAPSO products. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the SenAPSO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (MwAlxPySiz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about. 6 and more preferably from greater than zero to about 2; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300; and "w", "x", "y", and "z" represent the mole fractions of elements "M", aluminum, phosphorus and. silicon, respectively, and each has a value of at least 0.01, with the proviso that each "M" is present in a mole fraction of at least 0.01.
In a preferred embodiment the reaction mixture is selected such that the mole fractions "w", "x", "y" and " z " are generally defined as being within the limiting compositional values or points as follows: Mole Fraction
Point x y (z + w)
F 0.60 0.36 0.04
G 0.36 0.60 0.04
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "w", "x", "y" and "z" such that (w + x + y + z) = 1.00 mole. The SenAPSO molecular sieves are prepared by preparative techniques, and using sources of the elements "M" similar to those described for the other APSO molecular sieves described above and below.
AsAPSO MOLECULAR SIEVES The AsAPSO.molecular sieves of U.S. Serial No. 599,808, filed April 13, 1984, and U.S. Serial No. 845,484 filed March 31, 1986 have a framework structure of AsO2 n, AIO2-, PO2 + and SiO2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (AswAlxPySiz)O2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R '' present per mole of (AswAlxPySiz)O2 and has a value of zero to about 0.3, but is preferably not greater than 0.15.; and "w", "x", "y" and "z" represent the mole fractions of the elements arsenic, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. The mole fractions "w", "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of the AsAPSO molecular sieves, the values of w, x, y and z are as follows:
Mole Fraction
Point x y (z + w) a 0.60 0.38 0.02 b 0.38 0.60 0.02 c 0.01 0.60 0.39 d 0.01 0.39 0.60 e 0.39 0.01 0.60 f 0.60 0.01 0.39 In an especially preferred subclass of the AsAPSO molecular sieves, the values of w, x, y and z are as follows:
Mole Fraction
Point x y ( z + w) g 0.. 50 0 .40 0 . 10 h 0 .42 0 . 48 0 . 10 i 0 .38 0 .48 0 . 14 j 0 .38 0 .37 0 .25 k 0 .45 0 .30 0 .25 l 0 .50 0 .30 0 . 20
AsAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of arsenic, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the AsAPSO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 12 hours to about 10 days, have been observed. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the AsAPSO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR.: (AswAlχPySiz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 1.0; "b" has a value of from zero (0) -to about 500, preferably between about 2 and about 300, most preferably not greater than about 60; and "w", "x", "y"- and "z" represent the mole fractions of arsenic, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
In one embodiment the reaction mixture is selected such that the mole fractions "w", "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39 Especially preferred reaction mixtures are those containing from about 1 to about 2 total moles of silicon and arsenic, and from about 1 to about 2 moles of aluminum, per mole of phosphorus.
In the foregoing expression of the reaction composition, the reactants are normalized withrespect to the' total of "w", "x", "y" and "z" such that (w + x + y + z) = 1.00 mole. Molecular sieves containing arsenic, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents AsAPSO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare AsAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea Corporation for hydrated pseudoboehmite;
(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO2 .and 0.1 weight percent Na2O;
(d) H3PO4: 85 weight percent aqueous phosphoric acid;
(e) As2O5, arsenic (V) oxide;
(f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide; (h) Pr2NH: di-n-propylamine,
(C3H7)2NH; (i) Pr3N: tri-n-propylamine,
(C3H7)3N; (j) Quin: Quinuclidine, (C7H13N); (k) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH) ; (l) C-hex: cyclohexylamine; (m) TMAOH: tetramethylammonium hydroxide; (n) TPAOH: tetrapropylammonium hydroxide; and (o) DEEA: 2-diethylaminoethanol; (p) Tetraalkylorthosilicates, such as tetraethylorthosilicate.
Preparative Procedures AsAPSOs may be prepared by forming a starting reaction mixture by dissolving the arsenic (V) oxide and the H3PO4 in at least part of the water. To this solution the aluminum isopropoxide or CATAPAL is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture the templating agent and then the silica is added and the resulting mixture blended until a homogeneous mixture is observed. The mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure. BAPSO MOLECULAR SIEVES The BAPSO molecular sieves of U.S. Serial No. 600,177, filed April 13, 1984, and U.S. Serial No. 845,255 filed March 28, 1986 have a framework structure of BO2-, AlO2-, PO2 + and SiO2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (BwAlxPySiz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (BwAlxPySiz)O2 and has a value of zero to about 0.3, but is preferably not greater than 0.15; and "w", "x", "y" and "z" represent the mole fractions of the elements boron, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. The mole fractions "w", "x" , "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39 In a preferred subclass of the BAPSO molecular sieves, the values of w, x, y and z are as follows :
Mole Fraction
Point x y (z + w) a 0.60 0.38 0.02 b 0.38 0.60 0.02 c 0.01 0.60 0.39 d 0.01 0.39 0.60 e 0.39 0.01 0.60 f 0.60 0.01 0.39
In an especially preferred subclass of the BAPSO molecular sieves, the values of w, x, y and z are as follows:
Mole Fraction
Point x y (z + w) g 0.51 0.42 0.07 h 0.45 0.48 0.07 i 0.33 0.48 0.19 j 0.33 0.38 0.29 k 0.36 0.35 0.29
1 0.51 0.35 0.14
BAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of boron, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the BAPSO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 20 days, have been observed. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the BAPSO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (BwAlxPySiz)O2 : bH2O wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 0.5; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably not greater than about 20; and "w", "x", "y" and "z" represent the mole fractions of boron, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01. In one embodiment the reaction mixture is selected such that the mole fractions "w", "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows
Mole Fraction
Point x y (z + w)
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
Especially preferred reaction mixtures are those containing from about 1.0 to about 2 total moles of silicon and boron, and from about 0.75 to about 1.25 moles of aluminum, per mole of phosphorus. In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "w", "x", "y" and "z" such that (w + x + y + z) = 1.00 mole. Molecular sieves containing boron, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents BAPSO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare BAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea Corporation for hydrated pseudoboehmite; (c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO2 and 0.1 weight percent Na2O;
(d) H3PO4: 85 weight percent aqueous phosphoric acid;
(e) H3BO3, boric acid, and trialkyl borates;
(f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(h) Pr2NH: di-n-propylamine.
(C3H7)2NH; (i) Pr3N: tri-n-ρropylamine,
(C3H7)3N; (j) Quin: Quinuclidine, (C7H13N); (k) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH); (l) C-hex: cyclohexylamine; (m) TMAOH: tetramethylammonium hydroxide; (n) TPAOH: tetrapropylammonium hydroxide; and (o) DEEA: 2-diethylaminoethanol; (p) Tetraalkylorthosilicates, such as tetraethylorthosilicate. Preparative Procedures BAPSOs may be prepared by forming a starting reaction mixture by dissolving aluminum isopropoxide in an alcohol such as isopropanol, adding the H3PO4 and recovering the solid which precipitates. This solid is then added to water, and trialkylborate (for example trimethyl borate) added, followed by silica and the templating agent. This mixture is then blended until a homogeneous mixture is observed. The mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel. and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
BeAPSO MOLECULAR SIEVES The BeAPSO molecular sieves of U.S. Serial No. 600,176, filed April 13, 1984, and U.S. Serial No. 841,752 filed March 20, 1986 have a framework structure of BeO2 -2, AlO2-, PO2 + and SiO2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (BewAlxPySiz)02
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (BewAlxPySiz)O2 and has a value of zero to about 0.3, but is preferably not greater than 0.15; and "w", "x", "y" and "z" represent the mole fractions of the elements beryllium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. The mole fractions "w", "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of the BeAPSO molecular sieves, the values of w, x, y and z are as follows:
Mole Fraction
Point x y (z + w) a 0.60 0.38 0.02 b 0.38 0.60 0.02 c 0.01 0.60 0.39 d 0.01 0.39 0.60 e 0.39 0.01 0.60 f 0.60 0.01 0.39
BeAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of beryllium, silicon, aluminum and phosphorus, preferrably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under. autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the BeAPSO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 20 days, have been observed, with from 1 to 10 days being preferred. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the BeAPSO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (BewAlxPySiz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 0.5; "b" has a value of from zero (0) to about 500, preferably between about 2 to about 300, most preferably not greater than about 20; and "w", "x", "y" and "z " represent the mole fractions of beryllium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01,
In one embodiment the reaction mixture is selected such that the mole fractions "w", "x", "y" and " z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
F 0 . 60 0.38 0.02
G 0 .38 0 . 60 0 .02
H 0.01 0. 60 0.39
I 0 . 01 0.01 0 .98
J 0 . 60 0 . 01 0 .39
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "w", "x", "y" and "z" such that (w + x + y + z) = 1.00 mole. Molecular sieves containing beryllium, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents BeAPSO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare BeAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea Corporation for hydrated pseudoboehmite; (c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO2 and 0.1 weight percent Na2O;
(d) H3PO4: 85 weight percent aqueous phosphoric acid;
(e) beryllium sulfate, BeSO4;
(f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(h) Pr2NH: di-n-propylamine,
(C3H7)2NH; (i) Pr3N: tri-n-propylamine,
(C3H7)3N; (j) Quin: Quinuclidine, (C7H13N); (k) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH) ; (l) C-hex: cyclohexylamine; (m) TMAOH: tetramethylammonium hydroxide; (n) TPAOH: tetrapropylammonium hydroxide; and (o) DEEA: 2-diethylaminoethanol; (p) Tetraalkylorthosilicates, such as tetraethylorthosilicate.
Preparative Procedures BeAPSOs may be prepared by forming a starting solution by mixing H3PO4 in at least part of the water. To this solution is added beryllium sulfate (or another beryllium salt) and the resultant mixture stirred until a homogeneous solution is obtained. To this solution may be added successively the aluminum oxide, the silica and the templating agent, with the mixture being stirred . between each addition until it is homogeneous. Themixture is then placed in a lined (polytetra- fluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
CAPSO MOLECULAR SIEVES The CAPSO molecular sieves of U.S. Serial No. 599,830, filed April 13, 1984, and U.S. Serial No. 852,174 filed April 15, 1986 have a framework structure of CrO2 n, AIO2-, PO2 + and SiO2 tetrahedral units (where "n" is -1, 0 or +1) having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (CrwAlxPySiz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (CrwAlxPySiz)O2 and has a value of zero to about 0.3, but is preferably not greater than 0.15; and "w", "x" , "y" and "z" represent the mole fractions of the elements chromium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. The mole fractions "w", "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of the CAPSO molecular sieves, the values of w, x, y and z are as follows:
Mole Fraction
Point x y (z + w) a 0.60 0.38 0.02 b 0.38 0.60 0.02 c 0.01 0.60 0.39 d 0.01 0.39 0.60 e 0.39 0.01 0.60 f 0.60 0.01 0.39
In an especially preferred subclass of the CAPSO molecular sieves, the values of x and y in the above formula are each within the range of about 0.4 to 0.5 and (z+w) is in the range of about 0.02 to 0.15. Since the exact nature of the CAPSO molecular sieves is not clearly understood at present, although all are believed to contain CrO2 tetrahedra in the three-dimensional microporous crystal framework structure, it is advantageous to characterize the CAPSO molecular sieves by means of their chemical composition. This is due to the low level of chromium present in certain of the CAPSO molecular sieves prepared to date which makes it difficult to ascertain the exact nature of the interaction between chromium, aluminum, phosphorus and silicon. As a result, although it is believed that CrO2 tetrahedra are substituted isomorphously for AlO2, PO2 or SiO2 tetrahedra, it is appropriate to characterize certain CAPSO compositions by reference to their chemical composition in terms of the mole ratios of oxides.
CAPSO compositions are generally synthesized by hydrothermal crystallization from- a reaction mixture containing reactive sources of chromium, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the CAPSO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 20 days, and preferably about 1 to about 10 days, have been observed. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the CAPSO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (CrwAlxPySiz)O2 : bH2O wherein "R" is an organic templating agent; ."a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 0.5; "b" has a value of from zero (0). to about 500, preferably between about 2 and about 300, most preferably not greater than about 20; and "w", "x", "y" and " z " represent the mole fractions of chromium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
In one embodiment the reaction mixture is selected such that the mole fractions "w", "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y ( z + w)
F 0 . 60 0 . 38 0 . 02 G 0 .38 0 . 60 0 . 02 H 0 . 01 0 . 60 0 .39
I 0 . 01 0 . 01 0 . 98
J 0 . 60 0 .01 0 .39
Especially preferred reaction mixtures are those containing from about 0.3 to about 0.5 total moles of silicon and chromium, and from about 0.75 to about 1.25 moles of aluminum, per mole of phosphorus.
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "w", "x", "y" and "z" such that (w + x + y + z) = 1.00 mole. Molecular sieves containing chromium, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents CAPSO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare CAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea Corporation for hydrated pseudoboehmite;
(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO2 and 0.1 weight percent Na2O;
(d) H3PO4: 85 weight percent aqueous phosphoric acid; (e) chromium acetate, and chromium acetate hydroxide;
(f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(h) Pr2NH: di-n-propylamine,
(C3H7)2NH; (i) Pr3N: tri-n-propylamine,
(C3H7)3N; ( j ) Quin : Quinuclidine , (C7H13N) ; ( k) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH); (l) C-hex: eyelohexylamine; (m) TMAOH: tetramethylammpnium hydroxide; (π) TPAOH: tetrapropylammonium hydroxide; and (o) DEEA: 2-diethylaminoethanol; (p) Tetraalkylorthosilicates, such as tetraethylorthosilicate.
Preparative Procedures CAPSOs may be prepared by forming a starting solution by dissolving H3PO4 in at least part of the water. To this solution the aluminum isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture the silica, the chromium acetate or chromium acetate hydroxide and the templating agent are successively added and at each step the resulting mixture is blended until a homogeneous mixture is observed.
Alternatively, the water and aluminum isopropoxide may first be mixed, and then the silica, the chromium acetate or chromium acetate hydroxide, the. phosphoric acid and the templating agent added, and .again at each step the resulting mixture is blended until a homogeneous mixture is observed.
In either case, the mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
GaAPSO MOLECULAR SIEVES The GaAPSO molecular sieves of U.S. Serial No. 599,925, filed April 13, 1984, and U.S. Serial No. 845,985 filed March 31, 1986 have a framework structure of GaO2-, AlO2-, PO2 + and SiO2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (GawAlxPySiz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (GawAlxPySiz)O2 and has a value of zero to about 0.3, but is preferably not greater than 0.2; and "w", "x", "y" and "z" represent the mole fractions of the elements gallium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. The mole fractions "w", "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of the GaAPSO molecular sieves, the.values of w, x, y and z are as follows:
Mole Fraction
Point x y (z + w) a 0.60 0.38 0.02 b 0.38 0.60 0.02 c 0.01 0.60 0.39 d 0.01 0.39 0.60 e 0.39 0.01 0.60 f 0.60 0.01 0.39 In an especially preferred subclass of the GaAPSO molecular sieves, the values of w, x, y and z are as follows:
Mole Fraction
Point x y (z + w) g 0.45 0.40 0.15 h 0.33 0.52 0.15 i 0.20 0.52 0.28 j 0.20 0.45 0.35 k 0.36 0.29 0.35 l 0.45 0.29 0.26
GaAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of gallium, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the GaAPSO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 20 days, and preferably about 2 to about 15 days, have been observed. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the GaAPSO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows: aR : (GawAlxPySiz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 1.0; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably not greater than about 20; and "w", "x", "y" and "z" represent the mole fractions of gallium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
In one embodiment the reaction mixture is selected such that the mole fractions "w", "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39 Especially preferred reaction mixtures are those containing from about 0.5 to about 1.0 total moles of silicon and gallium, and from about 0.75 about 1.25 moles of aluminum, per mole of phosphorus.
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "w", "x", "y" and "z" such that (w + x + y + z) = 1.00 mole. Molecular sieves containing gallium, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents GaAPSO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare GaAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea Corporation for hydrated pseudoboehmite;
(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO2 and 0.1 weight percent Na2O;
(d) H3PO4: 85 weight percent aqueous phosphoric acid;
(e) gallium hydroxide, or gallium sulfate;
(f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide; (h) Pr2NH: di-n-propylamine,
(C3H7)2NH;
(i) Pr3N: tri-n-propylamine,
(C3H7)3N;
(j) Quin: Quinuclidine, (C7H13N);
(k) MQuin: Methyl. Quinuclidine hydroxide, (C7H13NCH3OH); (l) C-hex eyelohexylamine; (m) TMAOH tetramethylammonium hydroxide; (n) TPAOH tetrapropylammonium hydroxide; and (o) DEEA: 2-diethylaminoethanol; (p) Tetraalkylorthosilicates, such as tetraethylorthosilicate.
Preparative Procedures GaAPSOs may be prepared by forming a starting solution by dissolving H3PO4 in at least part of the water. To this solution the aluminum hydroxide or isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture is added a second solution prepared by adding silica to a solution containing the gallium hydroxide and the templating agent and then the combined mixture is blended until a homogeneous mixture is observed.
Alternatively, the templating agent may be added to the solution containing the phosphoric acid and water, and a solution of gallium sulfate in water added, followed by successive additions of silica and aluminum oxide and then the combined mixture is blended until a homogeneous mixture is observed. In either case, the mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
GeAPSO MOLECULAR SIEVES The GeAPSO molecular sieves of U.S. Serial No. 599,971, filed April 13, 1984, and U.S. Serial No. 852,175 filed April 15, 1986 have a framework structure of GeO2, AlO2-, PO2 + and SiO2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (GewAlxPySiz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (GewAlχPySiz)O2 and has a value of zero to about 0.3, but is preferably not greater than 0.15; and "w", "x", "y" and "z" represent the mole fractions of the elements geranium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. The mole fractions "w", "x", "y" and "z" are generally defined as being within the limited compositional values or points as follows:
Mole Fraction
Point x y (z + w)
A 0.60 0.38 0.02 B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of the GeAPSO molecular sieves, the values of w, x, y and z are as follows:
Mole Fraction
Point x y (z + w) a 0.60 0.38 0.02 b 0.38 0.60 0.02 c 0.01 0.60 0.39 d 0.01 0.39 0.60 e 0.39 0.01 0.60 f 0.60 0.01 0.39
In an especially preferred subclass of the GeAPSO molecular sieves, the values of w, x, y and z are as follows:
Mole Fraction
Point x y (z + w) g 0.60 0.35 0.05 h 0.47 0.48 0.05 i 0.40 0.48 0.12 j 0.40 0.36 0.24 k 0.46 0.30 0.24 l 0.60 0.30 0.10
GeAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of geranium, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the GeAPSO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 20 days, and preferably about 12 hours to about 7 days have been observed. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the GaAPSO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (GewAlxPySiz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 0.5; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably not greater than about 20; and desirably not greater than about 10; and "w", "x", "y" and "z" represent the mole fractions of germanium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
In one embodiment the reaction mixture is selected such that the mole fractions "w", "x" , "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y (z + w)
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
Especially preferred reaction mixtures are those containing from about 0.2 to about 0.3 total moles of silicon and germanium, and from about 0.75 about 1.25 moles of aluminum, per mole of phosphorus.
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "w", "x", "y" and "z" such that (w + x + y + z) = 1.00 mole. Molecular sieves containing germanium, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows: Preparative Reagents GeAPSO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare GeAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea Corporation for hydrated pseudoboehmite;
(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO2 and 0.1 weight percent Na2O;
(d) H3PO.4: 85 weight percent aqueous phosphoric acid;
(e) germanium tetrachloride or germanium ethoxide;
(f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(h) Pr2NH: di-n-propylamine,
(C3H7)2NH; (i) Pr3N: tri-n-propylamine,
(C3H7)3N; (j) Quin: Quinuclidine, (C7H13N) ; (k) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH) ; (l) C-hex: eyelohexylamine; (m) TMAOH: tetramethy1ammonium hydroxide; (n) TPAOH: tetrapropylammonium hydroxide; and (o) DEEA: 2-diethylaminoethanol; (p) Tetraalkylorthosilicates, such as tetraethylorthosilicate; and (q) aluminum chlorhydrol.
Preparative Procedures In some cases, it may be advantageous, when synthesizing the GeAPSO compositions, to first combine sources of germanium and aluminum, or of germanium, aluminum and silicon, to form a mixed germanium/aluminum or germanium/aluminum/silicon compound (this compound being typically a mixed oxide) and thereafter to combine this mixed compound with a source of phosphorus to form the final GeAPSO composition. Such mixed oxides may be prepared for example by hydrolyzing aqueous solutions containing germanium tetrachloride and aluminum chlorhydrol, or germanium ethoxide, tetraethylorthosilicate, and aluminum tri-sec-butoxide.
GeAPSOs may be prepared by forming a starting solution by dissolving H3PO4 in at least part of the water. To this solution the aluminum isopropoxide or CATAPAL is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture is the templating agent and then a solution containing tetraethylorthosilicate and germanium ethoxide, and the resulting mixture blended until a homogeneous mixture is observed.
Alternatively, the phosphoric acid may first be mixed with the templating agent, and then a solution containing tetraethylorthosilicate and germanium ethoxide combined with the phosphoric acid/templating agent solution. Then the aluminum oxide is added and the resultant mixture blended until homogeneous.
In a third procedure, the phosphoric acid may first be mixed with the templating agent and water, and to the resultant solution is added the solid aluminum/ silicon/germanium mixed oxide prepared as described above. The resultant mixture is then blended until homogeneous.
Whichever procedure is adopted, the final mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
LiAPSO MOLECULAR SIEVES The LiAPSO molecular sieves of U.S. Serial No. 599,952, filed April 13, 1984, and U.S. Serial No. 847,227 filed April 2, 1986 have a framework structure of LiO2 -3, AlO2-, PO2 + and SiO2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: mR : (LiwAlχPySiz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (LiwAlχPySiz)O2 and has a value of zero to about 0.3, but is preferably not greater than 0.15; and "w", "x" , "y" and "z" represent the mole fractions of the elements lithium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. The mole fractions "w", "x", "y" and "z" are generally defined as being within the limiting compositional values or points, as follows:
Mole Fraction
Point x y (z + w)
A 0.60 0.38 0.02
B 0.38 0.60 0.02
C 0.01 0.60 0.39
D 0.01 0.01 0.98
E 0.60 0.01 0.39
In a preferred subclass of the LiAPSO molecular sieves, the. values of w, x, y and z are as follows:
Mole Fraction
Point x y (z + w) a 0.60 0.38 0.02 b 0.38 0.60 0.02 c 0.01 0.60 0.39 d 0.01 0.39 0.60 e 0.39 0.01 0.60 f 0.60 0.01 0.39
In an especially preferred subclass of the LiAPSO molecular sieves, the value of w+z is not greater than about 0.20. Since the exact nature of the LiAPSO molecular sieves is not clearly understood at present, although all are believed to contain LiO2 tetrahedra in the three-dimensional microporous crystal framework structure, it is advantageous to characterize the LiAPSO molecular sieves by means of their chemical composition. This is due to the low level of lithium present in certain of the LiAPSO molecular sieves prepared to date which makes it difficult to ascertain the exact nature of the interaction between lithium, aluminum, phosphorus and silicon. As a result, although it is believed that LiO2 tetrahedra are substituted isomorphously for AlO2, PO2 or SiO2 tetrahedra, it is appropriate to characterize certain LiAPSO compositions by reference to their chemical composition in terms of the mole ratios of oxides.
LiAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of lithium, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the LiAPSO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 20 days, and preferably about 1 to about 10 days, have been observed. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the LiAPSO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows :
aR : (LiwAlχPySiz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 0.5; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably not greater than about 20, and most desirably not greater than about 10; and "w", "x", "y" and " z" represent the mole fractions of lithium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
In one embodiment the reaction mixture is selected such that the mole fractions "w", "x", "y" and " z " are generally defined as being within the limiting compositional values or points as follows: Mole Fraction
Point x y (z + w)
F 0.60 0.38 0.02
G 0.38 0.60 0.02
H 0.01 0.60 0.39
I 0.01 0.01 0.98
J 0.60 0.01 0.39
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "w", "x", "y" and "z" such that (w + x + y + z) = 1.00 mole. Molecular sieves containing lithium, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows :
Preparative Reagents LiAPSO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare LiAPSOs include:
(a) Alipro: aluminum isopropoxide;
(b) CATAPAL: Trademark of Condea Corporation for hydrated pseudoboehmite;
(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO2 and 0.1 weight percent Na2O;
(d) H3PO4 85 weight percent aqueous-phosphoric acid;
(e) lithium orthophosphate; (f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide; (g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide; (h) Pr2NH: di-n-propylamine,
(C3H7)2NH; (i) Pr2N: tri-n-propylamine,
(C3H7)3N.; (j) Quin: Quinuclidine, (C7H13N); (k) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH) ; (1) C-hex: cyclohexylamine; (m) TMAOH: tetramethylammonium hydroxide; (n) TPAOH: tetrapropylammonium hydroxide; and (o) DEEA: 2-diethylaminoethanol; (p) Tetraalkylorthosilicates, such as tetraethylorthosilicate.
Preparative Procedures LiAPSOs may be prepared by forming a starting reaction mixture mixing lithium phosphate and aluminum oxide, then adding the resultant mixture to the H3PO4. To the resultant mixture is added silica and the templating agent and the resulting mixture is blended until a homogeneous mixture is observed. The mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
AlPO4 ALUMINOPHOSPHATE MOLECULAR SIEVES
As already mentioned, the AlPO4 aluminophosphate molecular sieves are described in U.S. Patent No. 4,310,440 (incorporated herein by reference); these AlPO4 molecular sieves are also described in U.S. Serial No. 880,559, filed June 30, 1986.
MeAPO MOLECULAR SIEVES MeAPO molecular sieves are crystalline microporous aluminophosphates in which the substituent metal is one of a mixture of two or more divalent metals of the group magnesium, manganese, zinc and cobalt and are disclosed in U.S. Patent No. 4,567,029 (incorporated herein by reference).
FAPO MOLECULAR SIEVES As already mentioned, ferroaluminophosphates (FAPO's) are disclosed in U.S. Patent No. 4,554,143 (incorporated herein by reference).
TAPO MOLECULAR SIEVES As already mentioned, TAPO molecular sieves are disclosed in U.S. Patent No. 4,500,561 (incorporated herein by reference).
ELAPO MOLECULAR SIEVES "ELAPO" molecular sieves are a class of crystalline molecular sieves in which at least one element capable of forming a three-dimensional microporous framework forms crystal framework structures of AlO2-, PO2 + and MO2 n tetrahedral oxide units wherein "MO2 n" represents at least one different element (other than Al or P) present as tetrahedral oxide units "MO2 n" with charge "n" where "n" may be -3, -2, -1, 0 or +1. The members of this novel class of molecular sieve compositions have crystal framework structures of AlO2-, PO2 + and MO2 n tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (MxAlyPz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (MxAlyPz)O2; "M" represents at least one element capable of forming framework tetrahedral oxides; and "x", "y" and "z" represent the mole fraction of "M" , aluminum and phosphorus, respectively, present as tetrahedral oxides. "M" is at least one different (i.e., not aluminum, phosphorus or oxygen) element such that the molecular sieves contain at least one framework tetrahedral unit in addition to AIO2- and PO2 +. "M" is at least one element selected from the group consisting of arsenic, beryllium, boron, cobalt, chromium, gallium, germanium, iron, lithium, magnesium, manganese, titanium and zinc, subject to certain restrictions on the combinations of elements as will appear from the discussions of individual groups of ELAPOs below. ELAPOs and their preparation are disclosed in European Patent Application Serial No. 85104386.9, filed April 11, 1985 (EPC Publication No. 0158976, published October 13, 1985, incorporated herein by reference) and 85104388.5, filed April 11, 1985 (EPC Publication No. 158349, published October 16, 1985, incorporated herein by reference).
The "ELAPO" molecular sieves further include numerous species which are intended herein to be within the scope of the term "non-zeolitic molecular sieves" such being disclosed in the following copending and commonly assigned applications, incorporated herein by reference thereto [(A) following a serial number indicates that the application is abandoned, while (CIP) following a serial number indicates that the application is a continuation-in-part of the immediately preceding application, and (C) indicates that the application is a continuation of the immediately preceding application]:
U.S. Serial No. Filed NZMS
600,166(A) April 13, 1984 AsAPO
830,889(CIP) Feb. 19, 1986 AsAPO
599,812(A) April 13, 1984 BAPO
804,248(C)(A) Dec. 4, 1985 BAPO
029,540(CIP) March 24, 1987 BAPO
599,776(A) April 13, 1984 BeAPO
835,293(CIP) March 3, 1986 BeAPO
599,813(A) April 13, 1984 CAPO
830,756(CIP) Feb. 19, 1986 CAPO
599,771(A) April 13, 1984 GaAPO 830 , 890 (CIP) Feb . 19 , 1986 GaAPO
599,807(A) April 13, 1984 GeAPO
841,753(CIP) March 20, 1986 GeAPO
599,811(A) April 13, 1984 LiAPO
834,921(CIP) Feb. 28, 1986 LiAPO
600,171 April 13, 1984 FCAPO
(now U.S. Patent 4,686,093 issued August 11, 1987)
600, 172(A) April 13, 1984 ) ElAPO (M comprises two different
846,088(CIP) March 31, 1986 ) elements)
599,824(A) April 13, 1984 FeTiAPO
902,129(C) September 2, 1986 FeTiAPO
599,810(A) April 13, 1984 XAPO
902,020(C) September 2, 1986 XAPO
The disclosure of the patent listed in the foregoing table is incorporated herein by reference.
The ELAPO molecular sieves are generally referred to herein by the acronym "ELAPO" to designate element (s) "M" in a framework of AlO2-, PO2 + and Mo2 n tetrahedral oxide units. Actual class members will be identified by replacing the "EL" of the acronym with the elements present as MO2 n tetrahedral units. For example, "MgBeAPO" designates a molecular sieve comprised of AlO2-, PO2 +, MgO2 -2 and BeO2 -2 tetrahedral units. To identify various structural species which make up each of the subgeneric classes, each species is assigned a number and is identified as "ELAPO-i" wherein "i" is an integer. The given species designation is not intended to denote a similarity in structure to any other species denominated by a similar identification system.
The ELAPO molecular sieves comprise at least one additional element capable of forming framework tetrahedral oxide units (MO2 n) to form crystal framework structures with AlO2- and PO2 + tetrahedral oxide uni.ts wherein "M" represents at least one element capable of forming tetrahedral units "MO2 n" where "n" is -3, -2,
-1, 0 or +1 and is at least one element selected from the group consisting of arsenic, beryllium, boron, cobalt, chromium, gallium, germanium, iron, lithium, magnesium, manganese, titanium and zinc.
The ELAPO molecular sieves have crystalline three-dimensional microporous framework structures of AlO2-, PO2 + and MO2 n tetrahedral units and have an empirical chemical composition, on an anhydrous basis expressed by the formula: mR : (MxAlyPz)O2;
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (MxAlyPz)O2 and has a value of zero to about 0.3; "M" represents at least one element capable of forming framework tetrahedral oxides where "M" is at least one element selected from the group consisting of arsenic, beryllium, boron, cobalt, chromium, gallium, germanium, iron, lithium, magnesium, manganese, titanium and zinc. The relative amounts of element (s) "M", aluminum and phosphorous are expressed by the empirical chemical formula (anhydrous):
mR : (MχAlyPz)O2
where "x", "y" and "z" represent the mole fractions of said "M" aluminum and phosphorous. The individual mole fractions of each "M" (or when M denotes two or more elements, M1, M2 , M3 , etc.) may be represented by "x1", "x2", "x3"' etc. wherein "x1", "x2", and "x3" etc. represent the individual mole fractions of elements M1, M2, M3 , and etc. for "M" as above defined. The values of "x1", "x2", "x3", etc. are as defined for "x", hereinafter, where "x1" + "x2" + "x3" . . . = "x" and where x1, x2, x3 , etc. are each at least 0.01.
The ELAPO molecular sieves have crystalline three-dimensional microporous framework structures of MO2 n, AlO2- and PO2 + tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: mR : (MχAlyPz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents a molar amount of "R" present per mole of (MxAlyPz)O2 and has a value of zero to about 0.3; "M" represents at least one different element (other than Al or P) capable of forming framework tetrahedral oxides, as hereinbefore defined, and "x", "y" and "z" represent the mole fractions of "M", aluminum and phosphorous, respectively present as tetrahedral oxides; in general, said mole fractions "x" , "y" and "z" are within the following values for "x", "y" and "z", although as will appear hereinbelow, the limits for "x", "y" and "z" may vary slightly with the nature of the element "M" :
Mole Fraction
Point x y z
A 0.02 0.60 0.38
B 0.02 0.38 0.60
C 0.39 0.01 0.60
D 0.98 0.01 0.01
E 0.39 0.60 0.01
Also, in general, in a preferred sub-class of the ELAPOs of this invention, the values of "x", "y" and "z" in the formula above are within the following values for "x", "y" and "z", although again the relevent limits may vary somewhat with the nature of the element "M", as set forth hereinbelow:
Mole Fraction
Point x y z a 0.02 0.60 0.38 b 0.02 0.38 0.60 c 0.39 0.01 0.60 d 0.60 0.01 0.39 e 0.60 0.39 0.01 f 0.39 0.60 0.01 ELAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of the elements "M", aluminum and phosphorous, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between 50°C and 250°C, and preferably between 100°C and 200°C, until crystals of the ELAPO product are obtained, usually a period of from several hours to several weeks. Typical crystallization times are from about 2 hours to about 30 days with from about 2 hours to about 20 days being generally employed to obtain crystals of the ELAPO products. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the ELAPO compositions of the instant invention, it is in general preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (MxAlyPz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6; "b" has a value of from zero (0) to about 500, preferably between about 2 and 300; "M" represents at least one element, as above described, capable of forming tetrahedral oxide framework units, MO2 n, with AlO2- and PO2 + tetrahedral units; "n" has a value of -3, -2, -1, 0 or +1; and "x", "y" and "z" represent the mole fractions of "M", aluminum and phosphorous, respectively; "y" and "z" each have a value of at least 0.01 and "x" has a value of at least 0.01 with each element "M" having a mole fraction of at least 0.01. In general, the mole fractions "x", "y" and
"z" are preferably within the following values for "x", "y" and "z" :
Mole Fraction
Point x y z
F 0.01 0.60 0.39
G 0.-01 0.39 0.60
H 0.39 0.01 0.60
I 0.98 0.01 0.01
J 0.39 0.60 0.01
Further guidance concerning the preferred reaction mixtures for forming ELAPOs with various elements "M" will be given below.
In the foregoing expression of the reaction composition, the reactants are normalized with respect to a total of (M + Al + P) = (x + y + z) = 1.00 mole, whereas in other cases the reaction mixtures are expressed in terms of molar oxide ratios and may be normalized to 1.00 mole of P2O5 and/or Al2O3. This latter form is readily converted to the former form by routine calculations by dividing the total number of moles of "M", aluminum and phosphorous into the moles of each of "M", aluminum and phosphorous. The moles of template and water are similarly normalized by dividing by the total moles of "M", aluminum and phosphorous.
In forming the reaction mixture from which the instant molecular sieves are formed the organic templating agent can be any of those heretofore proposed for use in the synthesis of conventional zeolite aluminosilicates. In general these compounds contain elements of Group VA of the Periodic Table of Elements, particularly nitrogen, phosphorous, arsenic and antimony, preferably nitrogen or phosphorous and most preferably nitrogen, which compounds also contain at least one alkyl or aryl group having from 1 to 8 carbon atoms. Particularly preferred compounds for use as templating agents are the amines, quaternary phosphonium compounds and quaternary ammonium compounds, the latter two being represented generally by the formula R4X+ wherein "X" is nitrogen or phosphorous and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms. Polymeric quaternary ammonium salts such as [(C14H32N2) (OH)2]χ wherein "x" has a value of at least 2 are also suitably employed. The mono-, di- and tri-amines are advantageously utilized, either alone or in combination with a quaternary ammonium compound or other templating compound. Mixtures of two or more templating agents can either produce mixtures of the desired ELAPOs or the more strongly directing templating species may control the course of the reaction with the other templating species serving primarily to establish the pH conditions of the reaction gel.
Representative templating agents include tetramethylammonium, tetraethylammonium, tetrapropylammonium or tetrabutylammonium ions; tetrapentylammonium ion; di-n-propylamine; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methylpyridine; N,N-dimethylbenzylamine; N,N-dimethylethanolamine; choline; N,N'-dimethylρiρerazine; 1,4-diazabicyclo (2,2,2,) octane; N-methyldiethanolamine; N-methylethanolamine; N-methylpiperidine; 3-methylρiρeridine; n-methylcyclohexylamine; 3-methylρyridine; 4-methylρyridine; quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion; di-n-butylamine, neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; and 2-imidazolidone. Not every templating agent will direct the formation of every of ELAPO, i.e., a single templating agent can, with proper manipulation of the reaction conditions, direct the formation of several ELAPO compositions, and a given ELAPO composition can be produced using several different templating agents. The phosphorous source is preferably phosphoric acid, but organic phosphates such as triethyl phosphate may be satisfactory, and so also may crystalline or amorphous aluminophosphates such as the AlPO4 composition of U.S. P. 4,310,440. Organophosphorous compounds, such as tetrabutylphosphonium bromide, do not apparently serve as reactive sources of phosphorous, but these compounds may function as templating agents. Conventional phosphorous salts such as sodium metaphosphate, may be used, at least in part, as the phosphorous source, but are not preferred.
The aluminum source is preferably either an aluminum alkoxide, such as aluminum isopropoxide, or pseudoboehmite. The crystalline or amorphous aluminophosphates which are a suitable source of phosphorous are, of course, also suitable sources of aluminum. Other sources of aluminum used in zeolite synthesis, such as gibbsite, sodium aluminate and aluminum trichloride, can be employed but are not preferred.
The element (s) "M" can be introduced into the reaction system in any form which permits the formation in situ of reactive form of the element, i.e., reactive to form the framework tetrahedral oxide unit of the element. The organic and inorganic salts, of "M" such as oxides, alkoxides, hydroxides, halides and carboxyates, may be employed including the chlorides, bromides, iodides, nitrates, sulfates, phosphates, acetates, formates, and alkoxides, including ethoxides, propoxides and the like. Specific preferred reagents for introducing various elements "M" are discussed hereinbelow.
While not essential to the synthesis of ELAPO compositions, stirring or other moderate agitation of the reaction mixture and/or seeding the reaction mixture with seed crystals of either the ELAPO species to be produced or a topologically similar species, such as aluminophosphate, alumino-silicate or molecular sieve compositions, facilitates the crystallization procedure.
After crystallization the ELAPO product may be isolated and advantageously washed with water and dried in air. The as-synthesized ELAPO generally contains within its internal pore system at least one form of the templating agent employed in its formation. Most commonly the organic moiety is present, at least in part, as a charge-balancing cation as is generally the case with as-synthesized aluminosilicate zeolites prepared from organic-containing reaction systems. It is possible, however, that some or all of the organic moiety is an occluded molecular species in a particular ELAPO species. As a general rule the templating agent, and hence the occluded organic species, is too large to move freely through the pore system of the ELAPO product and must be removed by calcining the ELAPO at temperatures of 200°C to 700°C to thermally degrade the organic species. In a few instances the pores of the ELAPO product are sufficiently large to permit transport of the templating agent, particularly if the latter is a small molecule, and accordingly complete or partial removal thereof can be accomplished by conventional desorption procedures such as carried out in the case of zeolites. It will be understood that the term "as-synthesized" as used herein does not include the condition of the ELAPO phase wherein the organic moiety occupying the intracrystalline pore system as a result of the hydrothermal crystallization process has been reduced by post-synthesis . treatment such that the value of "m" in the composition formula:
mR : (MxAlyPz)O2
has a value of less than 0.02. The other symbols of the formula are as defined hereinabove. In those, preparations in which an alkoxide is employed as the source of element "M", aluminum or phosphorous, the corresponding alcohol is necessarily present in the reaction mixture since it is a hydrolysis product of the alkoxide. It has not been determined whether this alcohol participates in the synthesis process as a templating agent. For the purposes of this application, however, this alcohol is arbitrarily omitted from the class of templating agents, even if it is present in the as-synthesized ELAPO material.
Since the present ELAPO compositions are formed from MO2 n, AlO2- and PO2 + tetrahedral oxide units which, respectively, have a net charge of "n", (where "n" may be -3, -2, -1, 0 or +1), the matter of cation exchangeability is considerably more complicated than in the case of zeolitic molecular sieves in which, ideally, there is stoichiometric relationship between AlO2- tetrahedra and charge-balancing cations. In the instant compositions, an AlO2- tetrahedron can be balanced electrically either by association with a PO2 + tetrahedron or a simple cation such as an alkali metal cation, a proton (H+), a cation of "M" present in the reaction mixture, or an organic cation derived from the templating agent. Similarly, an MO2 n tetrahedron, where "n" is negative, can be balanced electrically by association with PO2 + tetrahedra, a cation of "M" present in the reaction mixture, organic cations derived from the templating agent, a simple cation such as an alkali metal cation, or other divalent or polyvalent metal cation, a proton (H+), or anions of cations introduced from an extraneous source. It has also been postulated that non-adjacent AlO2- and PO2 + tetrahedral pairs can be balanced by Na+ and OH- respectively (Flanigen and Grose, Molecular Sieve Zeolites-I, ACS, Washington, D.C. (1971).
AsAPO MOLECULAR SIEVES The AsAPO molecular sieves of U.S. Serial No. 600,166, filed April 13, 1984, and U.S. Serial No. 830,889 filed February 19, 1986 have a framework structure of AsO2 n, AlO2- and PO2 + tetrahedral units (where "n" is -1 or +1) and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (AsxAlyPz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R present per mole of (AsxAlyPz)O2 and has a value of zero to about 0.3, but is preferably not greater than 0.15; and "x", "y" and "z" represent the mole fractions of the elements arsenic, aluminum and phosphorous, respectively, present as tetrahedral oxides. The mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
A 0.01 0.60 0.39
B 0.01 0.39 0.60
C 0.39 0.01 0.60
D 0.60 0.01 0.39
E 0.60 0.39 0.01
F 0.39 0.60 0.01
There are two preferred subclasses of the AsAPO molecular sieves, depending upon whether the value of "n" is -1 or +1 (i.e. whether the arsenic is trivalent or pentavalent), it being understood that mixtures of such are permitted in a given AsAPO. When "n" is -1, the preferred values of x, y and z are within the limiting compositional values or points as follows:
Mole Fraction
Point x y z a 0.01 0.59 0.40 b 0.01 0.39 0.60 c 0.39 0.01 0.60 d 0.59 0.01 0.40 When "n" is +1, the preferred values of x, y and z are within the limiting compositional values or points as follows:
Mole Fraction
Point x y z e 0.01 0.60 0.39 f 0.01 0.40 0.59 g 0.59 0.40 0.01 h 0.39 0.60 0.01
In an especially preferred subclass of the AsAPO molecular sieves in which "n" = +1, the values of x, y and z are as follows:
Mole Fraction
Point x y z i 0.03 0.52 0.45 j 0.03 0.45 0.52 k 0.08 0.40 0.52
1 0.33 0.40 0.27 m 0.33 0.41 0.26 n 0.22 0.52 0.26
AsAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of arsenic, aluminum and phosphorous, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, .preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the AsAPO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 2 hours to about 20 days, and preferably about 12 hours to about 7 days, have been observed. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the AsAPO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (AsxAlyPz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 0.5; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably not greater than about 20; and "x", "y" and "z" represent the mole fractions of arsenic, aluminum and phosphorous, respectively, and each has a value of at least 0.01.
In one embodiment the reaction mixture is selected such that the mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
G 0.01 0.60 0.39
H 0.01 0.39 0.60
I 0.39 0.01 0.60
J 0.98 0.01 0.01
K 0.39 0.60 0.01
Especially preferred reaction mixtures are those wherein the mole fractions "x", "y" and "z" are within the limiting compositional values or points as follows:
Mole Fraction
Point x y z a 0.20 0.55 0.25 b 0.20 0.50 0.30 c 0.30 0.40 0.30 d 0.40 0.40 0.20 e 0.40 0.50 0.10 f 0.35 0.55 0.10
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "x", "y" and "z" such that (x + y + z) = 1.00 mole. Molecular sieve containing arsenic, aluminum and phosphorous as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents AsAPO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare AsAPOs include:
(a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous phosphoric acid;
(d) As2O5, arsenic (V) oxide;
(e) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(g) Pr2NH: di-n-propylamine.
(C3H7)2NH; (h) Pr3N: tri-n-propylamine,
(C3H7)3N; (i) Quin: Quinuclidine, (C7H13N); (j) MQuin: Methyl Quinuclidine hydroxide,
(C7H13 NCH3OH); (k) C-hex: cyclohexylamine; (l) TMAOH: tetramethylammonium hydroxide (m) TPAOH: tetrapropylamrnonium hydroxide; and (n) DEEA: 2-diethylaminoethano.. Preparative Procedures AsAPOs may be prepared by forming a starting reaction mixture by dissolving the arsenic (V) oxide and the H3PO4 in at least part of the water. To this solution the aluminum oxide or isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture the templating agent and the resulting mixture blended until a homogeneous mixture is observed. The mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
BAPO MOLECULAR SIEVES The BAPO molecular sieves of U.S. Serial No. 599,812, filed April 13, 1984, U.S. Serial No. 804,248, filed December 4, 1985, and U.S. Serial No. 029,540, filed March 24, 1987, have a framework structure of BO2 -, AlO2 - and PO2 + tetrahedral units and have an empirical chemcial composition on an anhydrous basis expressed by the formula:
mR : (BxAlyPz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (BxAlyPz)O2 and has a value of zero to about 0.3, "x", "y" and "z" represent the mole fractions of the elements boron, aluminum and phosphorus, respectively, present as tetrahedral oxides. The more fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
A 0.01 0.60 0.39
B 0.01 0.39 0.60
C 0.39 0.01 0.60
D 0.60 0.01 0.39
E 0.60 0.39 0.01
F 0.39 0.60 0.01
In a preferred subclass of the BAPO molecular sieves the values of x, y, and z are within the limiting compositional values or points as follows:
Mole Fraction
Point x y z a 0.01 0.59 0.40 b 0.01 0.39 0.60 c 0.39 0.01 0.60 d 0.59 0.01 0.40
An especially preferred subclass of the BAPO molecular sieves are those in which the mole fraction, "x", of boron is not greater than about 0.3. BAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of boron, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal . The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the BAPO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 14 days, and preferably about 1 to about 7 days, have been observed. The product is recovered by any convient method such as centrifugation or filtration.
In synthesizing the BAPO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (BxAlyPz)O2 bH2O
where "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and is an effective amount preferably within the range of greater than zero (0) to about 6, and most preferably not more than about 1.0; "b" has a value of from zero (0) to about 500,' preferably between about 2 and about 300, desirably not greater than about 20, and most desirably not greater than about 10; and "x", "y" and "z" represent the mole fractions of boron, aluminum and phosphorus, respectively, and each has a value of at least 0.01.
In one embodiment the reaction mixture is selected such that the. mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
G 0.01 0.60 0.39
H 0.01 0.39 0.60
I 0.39 0.01 0.60
J 0.98 0.01 0.01
K 0.39 0.60 0.01
Especially preferred reaction mixtures are those containing from 0.5 to 2.0 moles of B2O3 and from 0.75 to 1.25 moles of Al2O3 for each mole of P 2O5.
In the foregoing expression, of the reaction composition, the reactants are normalized with respect to the total of "x", "y" and "z" such that (x + y + z) = 1.00 mole.
The exact nature of the BAPO molecular sieves is not entirely understood at present, although all are believed to contain BO2, AlO2 and PO2 tetrahedra in the three-dimensional microporous framework structure. The low level of boron present in some of the instant molecular sieves makes it difficult to ascertain the exact nature of the interactions among boron, aluminum and phosphorus. As a result, although it is believed that BO2 tetrahedra are present in the three-dimensional microporous framework structure, it is appropriate to characterize certain BAPO compositions in terms of the molar ratios of oxides. Molecular sieves containing boron, aluminum and phosphorus as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents BAPO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare BAPOs include:
(a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 wieght percent aqueous phosphoric acid;
(d) boric acid or trimethylborate;
(e) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(g) Pr2NH: di-n-propylamine, (C3H7)2NH;
(h) Pr3N: tri-n-propylamine, (C3H7)3N;
(i) Quin: Quinulidine, (C7H13N), (j) MQuin: Methyl Quinuclide hydroxide.
(C7H13NCH3OH);
(k) c-hex: eyelohexylamine;
(l) TMAOH: tetramethylammonium hydroxide; (m) TPAOH: tetrapropylarnmonium hydroxide; and
(n) DEEA: 2-diethylaminoethanol.
Preparative Procedures In the preferred method of synthesizing the BAPO compositions, one first combines sources of boron, aluminum and phosphorus to form an amorphous material containing all three elements, and thereafter heats the amorphous material to produce a crystalline BAPO molecular sieve. It is not necessary that the total quantities of the reactive sources of boron, aluminum and phosphorus to be used in the final reaction mixture be present in the amorphous material, since additional quantities of the elements can be added during the later heat treatment; in particular, it has been found convenient to add additional quantities of phosphorus to the amorphous material before the heat treatment. The preliminary formation of the amorphous material assists in the incorporation of the boron into the final molecular sieve.
For example, BAPOs may be prepared by forming a solution of boric acid in a methanolic solution of the templating agent, then adding a hydrated aluminosphosphate and water and stirring to form a homogeneous reaction slurry. This slurry is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
BeAPO MOLECULAR SIEVES The BeAPO molecular sieves of U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial
No. 835,293 filed March 3, 1986 have a framework structure of BeO2 -2, AlO2- and PO2 + tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (BeχAlyPz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (BexAlyPz)O2 and has a value of zero to about 0.3, but is preferably not greater than 0.15; and "x", "y" and "z" represent the mole fractions of the elements beryllium, aluminum and phosphorus, respectively, present as tetrahedral oxides. The mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows: Mole Fraction
Point x y z
A 0.01 0.60 0.39
B 0.01 0.39 0.60
C 0.39 0.01 0.60
D 0.60 0.01 0.39
E 0.60 0.39 0.01
F 0.39 0.60 0.01
In a preferred subclass of the BeAPO molecular sieves the values of x, y and z are within the limiting compositional values or points as follows:
Mole Fraction
Point x y z a 0.01 0.60 0.39 b 0.01 0.39 0.60 c 0.35 0.05 0.60 d 0.35 0.60 0.05
In an especially preferred subclass of the BeAPO molecular sieves the values of x, y and z are as follows:
Mole Fraction
Point x y z e 0.02 0.46 0.52 f 0.10 0.38 0.52 g 0.10 0.46 0.44 BeAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of beryllium, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a .sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250ºC, and preferably between about 100°C and about 200°C until crystals of the BeAPO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 14 days, and preferably about 1 to about 7 days, have been observed. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the BeAPO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (BexAlyPz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 1.5; "b" has a value of from zero (0) to about 500, preferably between about .2 and about 300, most preferably not greater than about 50; and "x", "y" and "z" represent the mole fractions of beryllium, aluminum and phosphorus, respectively, and each has a value of at least 0.01.
In one embodiment the reaction mixture is selected such that the mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
G 0.01 0.60 0.39
H 0.01 0.39 0.60
I 0.39 0.01 0.60
J 0.98 0.01 0.01
K 0.39 0.60 0.01
Especially preferred reaction mixtures are those wherein the mole fractions "x", "y" and "z" are within the limiting compositional values or points as follows:
Mole Fraction
Point x y z g 0.04 0.46 0.50 h 0.16 0.34 0.50 i 0.17 0.34 0.49 j 0.17 0.43 0.40 k 0.14 0.46 0.40 In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "x", "y" and "z" such that (x + y + z) = 1.00 mole. Molecular sieves containing beryllium, aluminum and phosphorus as framework tetrahdedral oxide units are prepared as follows:
Preparative Reagents BeAPO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare BeAPOs include:
(a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous phosphoric acid;
(d) beryllium sulfate; (e) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(g) Pr2NH: di-n-propylamine, (C3H7)2NH;
(h) Pr3N: tri-n-propylamine,
(C3H7)3N; (i) Quin: Quinuclidine, (C7H13N); (j) MQuin: Methyl Quinuclide hydroxide,
(C7H13NCH3OH) ; (k) C-hex: cyclohexylamine; (1) TMAOH: tetramethylammonium hydroxide; (m) TPAOH: tetrapropylammonium hydroxide; and (n) DEEA: 2-diethylaminoethanol.
Preparative Procedures BeAPOs may be prepared by forming a starting reaction mixture by dissolving the beryllium sulfate and the H3PO4 in at least part of the water. To this solution the aluminum oxide or isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture the templating agent and the resulting mixture blended until a homogeneous mixture is observed. The mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
CAPO MOLECULAR SIEVES The CAPO molecular sieves, of U.S. Serial No. 599,813, filed April 13, 1984, and U.S. Serial No. 830,756 filed February 19, 1986 have a framework structure of CrO2 n, AlO2- and PO2 + tetrahedral units (where "n" is -1, 0 or +1) and have an empirical chemical composition on an anhydrous basis expressed by the formula
mR : (CrxAlyPz)O2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (CrxAlyPz)O2 and has a value of zero to about 0.3, but is preferably not greater than 0.15; and "x", "y" and "z" represent the mole fractions of the elements chromium, aluminum and phosphorus, respectively, present as tetrahedral oxides. When "n" is -1 or +1, the mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
A 0.01 0.60 0.39
B 0.01 0.39 0.60
C 0.39 0.01 0.60
D 0.60 0.01 0.39
E 0.60 0.39 0.01
F 0.39 0.60 0.01
When "n" is 0, the mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
G 0.01 0.60 0.39
H 0.01 0.47 0.52
I 0.94 0.01 0.05
J 0.98 0.01 0.01
K 0.39 0.60 0.01 There are three preferred subclasses of the CAPO molecular sieves, depending upon whether the value of "n" is -1, 0 or +1 (i.e. whether the chromium has an oxidation number of 3, 4 or 5), it being understood that mixtures of such are permitted in a given CAPO. When "n" is -1, the preferred values of x, y and z are within the limiting compositional values or points as follows:
Mole Fraction
Point x y z a 0.01 0.59 0.40 b 0.01 0.39 0.60 c 0.39 0.01 0.60 d 0.59 0.01 0.40
In an especially preferred subclass of these CAPO molecular sieves in which "n" = -1, the values of x, y and z are as follows:
Mole Fraction
Point x y z n 0.01 0.52 0.47
0 0.01 0.42 0.57
P 0.03 0.40 0.57 q 0.07 0.40 0.53 r 0.07 0.47 0.46 s 0.02 0.52 0.46
When "n" is 0, the preferred values of x, y and z are within the limiting compositional values or points as follows: Mole Fraction
Point X y z e 0.01 0.60 0.39 f 0.01 0.47 0.52 g 0.50 0.225 0.275 h 0.50 0.40 0.10 i 0.30 0.60 0.10
When "n" is +1, the preferred values of x, y and z are within the limiting compositional values or points as follows:
Mole Fraction
Point X y z j 0.01 0.60 0.39 k 0.01 0.40 0.59 l 0.59 0.40 0.01 m 0.39 0.60 0.10
Since the exact nature of the CAPO molecular sieves is not clearly understood at present, although all are believed to contain CrO2 tetrahedra in the three-dimensional microporous crystal framework structure, it is advantageous to characterize the CAPO molecular sieves by means of their chemical composition. This is due to the low level of chromium present in certain of the CAPO molecular sieves prepared to date which makes it difficult to ascertain the exact nature of the interaction between chromium, aluminum and phosphorous. As a result, although it is believed that CrO2 tetrahedra are substituted isomorphously for AlO2 or PO2 tetrahedra, it is appropriate to. characterize certain CAPO compositions by reference to their chemical composition in terms of the mole ratios of oxides.
CAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of chromium, aluminum and phosphoro.us, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the CAPO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 2 hours to about 20 days, and preferably about 1 to about 10 days, have been observed. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the CAPO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (CrxAl Pz)O2 : bH2O wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 0.6; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably not greater than about 20; and "x", "y" and "z" represent the mole fractions of chromium, aluminum and phosphorous, respectively, and each has a value of at least 0.01.
In one embodiment the reaction mixture is selected such that the mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
L 0.01 0.60 0.39
M 0.01 0.39 0.60
N 0.39 0.01 0.60
O 0.98 0.01 0.01
P 0.39 0.60 0.01
Especially preferred reaction mixtures are those containing from about 0.1 to about 0.4 moles of chromium, and from about 0.75 to about 1.25 moles of aluminum, per mole of phosphorous.
In the foregoing expression of the reaction composition, the reactants are normalized .with respect to the total of "x", "y" and "z" such that (x + y + z) = 1.00 mole. Molecular sieves containing chromium, aluminum and phosphorous as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents CAPO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare CAPOs include:
(a) aluminum isopropoxide, or aluminum chlorhydrol;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous phosphoric acid;
(d) chromium (III) orthophosphate, chromium (III) acetate and chromium acetate hydroxide,
(Cr3 (OH)2(CH3COO)7);
(e) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(g) Pr2NH: di-n-propylamine, (C3H7)2NH;
(h) Pr3N: tri-n-propylamine,
(C3H7)3N; (i) Quin: Quinuclidine, (C7H13N); (j) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH); (k) C-hex: cyclohexylamine; (l) TMAOH: tetramethylammonium hydroxide: (m) TPAOH: tetrapropylammonium hydroxide; and (n) DEEA: 2-diethylaminoethanol.
Preparative Procedures
CAPOs may be prepared by forming a starting reaction mixture by adding aluminum chlorhydrol or aluminum oxide to a solution of chromium acetate hydroxide in water, then adding successively phosphoric acid and the templating agent. Between each addition, and after formation of the final mixture, the mixture is blended until a homogeneous mixture is observed.
Alternatively, the phosphoric acid may be mixed with at least part of the water, and aluminum oxide or isopropoxide mixed in. A solution of chromium acetate hydroxide is then added, followed by the templating agent, and the resultant mixture mixed until homogeneous.
In a third procedure, amorphous chromium phosphate is ground dry with aluminum oxide and the resultant dry mixture added to an aqueous solution of phosphoric acid in an ice bath. The templating agent is then added, and the final mixture mixed until homogenous.
Whichever technique is employed to produce the reaction mixture, this mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
GaAPO MOLECULAR SIEVES The GaAPO molecular sieves of U.S. Serial No. 599,771, filed April 13, 1984, and U.S. Serial No. 830,890 filed February 19, 1986 have a framework structure of GaO2-, AlO2 and PO2 tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (GaxAlyPz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (GaxAlyPz)O2 and has a value of zero to about 0.3, but is preferably not greater than 0.15; and "x", "y" and "z" represent the mole fractions of the elements gallium, aluminum and phosphorous, respectively, present as tetrahedral oxides. The mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
A 0.01 0.60 0.39
B 0.01 0.34 0.65
C 0.34 0.01 0.65
D 0.60 0.01 0.39
E 0.60 0.39 0.01
F 0.39 0.60 0.01 In general, the value ,of "z" in the GaAPO molecular sieves is not greater than about 0.60.
In a preferred subclass of the GaAPO molecular sieves the values of x, y and z are within the limiting compositional values or points as follows:
Mole Fraction
Point x y z a 0.01 0.59 0.40 b 0.01 0.34 0.65 c 0.34 0.01 0.65 d 0.59 0.01 0.40
In an especially preferred subclass of the GaAPO molecular sieves the values of x, y and z are as follows:
Mole Fraction
Point x y z e 0.03 0.52 0.45 f 0.03 0.33 0.64 g 0.16 0.20 0.64 h 0.25 0.20 0.55 i 0.25 0.33 0.42 j 0.06 0.52 0.42
GaAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of gallium, aluminum and phosphorous, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the GaAPO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 20 days, and preferably about 1 to about 7 days, have been observed. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the GaAPO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (GaxAlyPz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 1.0; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably between about 2 and 20; and "x", "y" and "z" represent the mole fractions of gallium, aluminum and phosphorous, respectively, and each has a value of at least 0.01.
In one embodiment the reaction mixture is selected such that the mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
G 0.01 0.60 0.39
H 0.01 0.39 0.60
I 0.39 0.01 0.60
J 0.98 0.01 0.01
K 0.39 0.60 0.01
Especially preferred reaction mixtures are those containing from 0.2 to 0.5 mole of Ga2O3 and from 0.3 to 1 mole of Al2O3 for each mole of
P2O5.
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "x", "y" and "z" such that (x + y + z) = 1.00 mole. Molecular sieves containing gallium, aluminum and phosphorous as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents GaAPO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare GaAPOs include: (a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous phosphoric acid;
(d) gallium sulfate or gallium (III) hydroxide;
(e) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(g) Pr2NH: di-n-propylamine, (C3H7)2NH;
(h) Pr3N: tri-n-propylamine,
(C3H7)3N; (i) Quin: Quinuclidine, (C7H13N) ; (j) MQuin: Methyl Quinuclidine hydroxide,
(C7H13 NCH3OH); (k) C-hex: cyclohexylamine; (l) TMAOH: tetramethylammonium hydroxide; (m) TPAOH: tetrapropylammonium hydroxide; and (n) DEEA: 2-diethylaminoethanol.
Preparative Procedures GaAPOs may be prepared by forming a starting reaction mixture by mixing the phosphoric acid with at least part of the water. To this solution the aluminum oxide or isopropoxide is added. This mixture is then blended until a homogenous mixture is observed. To this mixture the gallium sulfate or gallium hydroxide and the templating agent are successively added and the resulting mixture blended until a homogeneous mixture is observed.
Alternatively, the aluminum oxide may be mixed with a solution of the gallium sulfate or hydroxide, and then the phosphoric acid and the templating agent successively added. The resulting mixture is then blended until a homogeneous mixture is observed.
In a third process, the templating agent may be dissolved in water, the gallium hydroxide or sulfate added with stirring, a solution of the phosphoric acid added, and finally the aluminum oxide mixed in. The resulting mixture is then blended until a homogeneous mixture is observed.
Whichever technique is employed to form the reaction mixture, the mixture is then placed in .a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressures.
GeAPO MOLECULAR SIEVES The GeAPO molecular sieves of U.S. Serial No. 599,807, filed April 13, 1984, and U.S. Serial No. 841,753 filed March 20, 1986 have a framework structure of GeO2, AIO2- and PO2 + tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula: mR : (GexAlyPz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (GeχAlyPz)O2 and has a value of zero to. about 0.3, but is preferably not greater than 0.2; and "x", "y" and "z" represent the mole fractions of the elements germanium, aluminum and phosphorous, respectively, present as tetrahedral oxides. The mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
A 0.01 0.60 0.39
B 0.01 0.47 0.52
C 0.94 0.01 0.05
D 0.98 0.01 0.01
E 0.39 0.60 0.01
In a preferred subclass of the GeAPO molecular sieves the values of x, y and z are within the limiting compositional values or points as follows:
Mole Fraction
Point x y z a 0.01 0.60 0.39 b 0.01 0.47 0.52 c 0 . 50 0 . 225 0 . 275 d 0 . 50 0 . 40 0 . 10 e 0 . 30 0 . 60 0 . 10
An especially preferred subclass of the GeAPO molecular sieves are those in which the value of "x" is not greater than about 0.13.
.GeAPO compositions .are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of germanium, aluminum and phosphorous, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the GeAPO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 2 hours to about 20 days, and preferably about 1 to about 10 days, have been observed. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the GeAPO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows: aR : (GexAlyPz)O2 : bH2O wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 0.6; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably between about 10 and about 60; and "x", "y" and "z" represent the mole fractions of germanium, aluminum and phosphorous, respectively, and each has a value of at least 0.01.
In one embodiment the reaction mixture is selected such that the mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
F 0.01 0.60 0.39
G 0.01 0.39 0.60
H 0.39 0.01 0.60
I 0.98 0.01 0.01
J 0.39 0.60 0.01
Especially preferred reaction mixtures are those containing from 0.2 to 0.4 mole of GeO2 and from 0.75 to 1.25 mole of Al2O3 for each mole of
P2O5.
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "x", "y" and "z" such that (x + y + z) = 1.00 mole. Molecular sieves containing germanium, aluminum and phosphorous as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents GeAPO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare GeAPOs include:
(a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous phosphoric acid;
(d) germanium tetrachloride, germanium ethoxide and germanium dioxide;
(e) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(g) Pr2NH: di-n-propylamine, (C3H7)2NH;
(h) Pr3N: tri-n-propylamine,
(C3H7)3N; (i) Quin: Quinuclidine, (C7H13N); (j) MQuin: Methyl Quinuclidine hydroxide,
(C7H13 NCH3OH); (k) C-hex: eyelohexylamine; (l) TMAOH: tetramethylammonium hydroxide; (m) TPAOH: tetrapropy1ammonium hydroxide; and (n) DEEA: 2-diethylaminoethanol. Preparative Procedures
In some cases, it may be advantageous, when synthesizing the GeAPO compositions, to first combine sources of germanium and aluminum, to form a mixed germanium/aluminum compound (this compound being typically a mixed oxide) and thereafter to combine this mixed compound with a source of phosphorous to form the final GeAPO composition. Such mixed oxides may be prepared for example by hydrolyzing aqueous solutions containing germanium tetrachloride and aluminum chlorhydrol, or aluminum tri-sec-butoxide.
GeAPOs may be prepared by forming a starting reaction mixture by mixing the phosphoric acid with at least part of the water. To this solution is added the mixed germanium/aluminum oxide prepared as described above. This mixture is then blended until a homogeneous mixture is observed. To this mixture the templating agent is added and the resulting mixture blended until a homogeneous mixture is observed.
Alternatively, to a solution of aluminum isopropoxide may be added germanium ethoxide. The resultant solution may optionally be dried to produce a mixed oxide. To the mixed solution or dried oxide are added successively the phosphoric acid and the templating agent. The resulting mixture is then blended until a homogeneous mixture is observed. In a third process, a solution is formed by dissolving the phosphoric acid in water, adding aluminum oxide or isopropoxide and mixing thoroughly. To the resultant mixture is added a solution containing the templating agent and germanium dioxide. The resulting mixture is then blended until a homogeneous mixture is observed.
Whichever technique is employed to form the reaction mixture, the -mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
LiAPO MOLECULAR SIEVES The LiAPO molecular sieves of U.S. Serial No. 599,811, filed April 13, 1984, and U.S. Serial No. 834,921 filed February 28, 1986 have a framework structure of LiO2 -3, AlO2- and PO2 + tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (LixAlyPz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (LixAlyPz)O2 and has a value of zero to about 0.3, but is preferably not greater than 0.15; and "x", "y" and "z" represent the mole fractions of the elements lithium, aluminum and phosphorous, respectively, present as tetrahedral oxides. The mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
A 0.01 0.60 0.39
B 0.01 0.39 0.60
C 0.39 0.01 0.60
D 0.60 0.01 0.39
E 0.60 0.39 0.01
F 0.39 0.60 0.01
In a preferred subclass of the LiAPO molecular sieves the values of x, y and z are within the limiting compositional values or points as follows:
Mole Fraction
Point x y z a 0.01 0.60 0.39 b 0.01 0.39 0.60 c 0.35 0.05 0.60 d 0.35 0.60 0.05
In an especially preferred subclass of the LiAPO molecular sieves the values of x, y and z are within the following limits: Mole Fraction
Point x y z e 0.01 0.52 0.47 f 0.01 0.47 0.52 g 0.03 0.45 0.52 h 0.10 0.45 0.45 i 0.10 0.49 0.41 j 0.07 0.52 0.41
LiAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of lithium, aluminum and phosphorous, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the LiAPO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 12 hours to about 5 days, have been observed. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the LiAPO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios a's follows:
aR : (LixAlyPz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than about 2; "b" has a value of from zero (0) to about 500, preferably between 2 and 300, most preferably not greater than about 40; and "x", "y" and "z" represent the mole fractions of lithium, aluminum and phosphorous, respectively, and each has a value of at least 0.01.
In one embodiment the reaction mixture is selected such that the mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
G 0.01 0.60 0.39
H 0.01 0.39 0.60
I 0.39 0.01 0.60
J 0.98 0.01 0.01
K 0.39 0.60 0.01
In an especially preferred subclass of the reaction mixtures, the values of "x", "y" and "z" are within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
1 0.03 0.50 0.47 m 0.03 0.45 0.52 n 0.08 0.40 0.52
0 0.10 0.40 0.50 g 0.04 0.50 0.46
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "x", "y" and "z" such that (x + y + z) = 1.00 mole.
Since the exact nature of the LiAPO molecular sieves is not clearly understood at present, although all are believed to contain LiO, tetrahedra in the three-dimensional microporous crystal framework structure, it is advantageous to characterize the LiAPO molecular sieves by means of their chemical composition. This is due to the low level of lithium present in certain of the LiAPO molecular sieves prepared to date which makes it difficult to ascertain the exact nature of the interaction between lithium, aluminum and phosphorous. As a result, although it is believed that LiO2 tetrahedra are substituted isomorphously for AIO2 or PO2 tetrahedra, it is appropriate to characterize certain LiAPO compositions by reference to their chemical composition in terms of the mole ratios of oxides. Molecular sieves containing lithium, aluminum and phosphorous as framework tetrahedral oxide units are prepared as followed:
Preparative Reagents LiAPO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare LiAPOs include:
(a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous phosphoric acid;
(d) lithium sulfate or lithium orthophosphate;
(e) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(g) Pr2NH: di-n-propylamine, (C3H7)2NH;
(h) Pr3N: tri-n-propylamine,
(C3H7)3N; (i) Quin: Quinuclidine, (C7H13N) ; (j) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH) ; (k) C-hex: eyelohexylamine; (l) TMAOH: tetramethylammonium hydroxide; (m) TPAOH: tetrapropylammonium hydroxide; and (n) DEEA: 2-diethylaminotthanol. Preparative Procedures LiAPOs may be prepared by forming a starting reaction mixture by suspending aluminum oxide in at least part of the water. To this mixture the templating agent is added. The resultant mixture is then blended until a homogeneous mixture is observed. To this mixture the lithium phosphate or sulfate is added and the resulting mixture blended until a homogeneous mixture is observed. Alternatively, an initial mixture may be formed by mixing aluminum oxide and lithium phosphate or sulfate. To the resultant mixture are added successively phosphoric acid and an aqueous solution of the templating agent, and the resulting mixture blended until a homogeneous mixture is observed.
In a third procedure, the phosphoric acid is mixed with at least part of the water, and the aluminum oxide is mixed in. To the resultant mixture are added lithium sulfate and the templating agent, and the resulting mixture blended until a homogeneous mixture is observed.
Whichever procedure is adopted to form the reaction mixture, the mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
FeTiAPO MOLECULAR SIEVES The FeTiAPO molecular sieves of U.S. Serial No. 599,824, filed April 13, 1984, and U.S. Serial No. 902,129 filed September 2, 1986 have three-dimensional microporous framework structures of FeO2 n, TiO2, AlO2- and PO2 + tetrahedral oxide units, where "n" is -2 or -1, and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (MxAlyPz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "M" represents iron and titanium; "m" represents the molar amount of "R" present per mole of (MxAlyPz)O2 and has a value of ze.ro (0) to about 0.3; and "x", "y" and~"z" represent the mole fractions of "M", aluminum and phosphorus, respectively present as tetrahedral oxides. The mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
A 0.02 0.60 0.38
B 0.02 0.38 0.60
C 0.39 0.01 0.60
D 0.98 0.01 0.01
E 0.39 0.60 0.01
In a preferred subclass of the FeTiAPO molecular sieves the values of x, y and z are within the limiting compositional values or points as follows:
Mole Fraction
Point x y z a 0.02 0.60 0.38 b 0.02 0.38 0.60 c 0.39 0.01 0.60 d 0.60 0.01 0.39 e 0.60 0.39 0.01 f 0.39 0.60 0.01
FeTiAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of iron, titanium, aluminum and phosphorous, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressμre vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the FeTiAPO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 12 hours to about 5 days, have been observed. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the FeTiAPO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (MxAlyPz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300; and "x", "y" and "z" represent the mole fractions of "M" (iron and titanium), aluminum and phosphorous, respectively, and each has a value of at least 0.01.
In one embodiment the reaction mixture is selected such that the mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
F 0.02 0.60 0.38
G 0.02 0.38 0.60
H 0.39 0.01 0.60
I 0.98 0.01 0.01
J 0.39 0.60 0.01 In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "x", "y" and "z" such that (x + y + z) = 1.00 mole.
Molecular sieves containing iron, titanium, aluminum and phosphorous as framework tetrahedral oxide units are prepared as follows:
Preparative Reagents FeTiAPO compositions may be prepared by using numerous reagents. The preferred sources of iron and titanium for preparing FeTiAPOs are the same as those for preparing the FeAPOs and TiAPOs already described above. Other reagents which may be employed to prepare FeTiAPOs include: (a) aluminum isopropoxide; (b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous phosphoric acid;
(d) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(e) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(f) Pr2NH: di-n-propylamine, (C3H7)2NH;
(g) Pr3N: tri-n-propylamine, (C3H7)3N;
(h) Quin: Quinuclidine, (C7H13N) ;
(i) MQuin: Methyl Quinuclidine hydroxide,
(C7H13NCH3OH) ; (j) C-hex: cyclohexylamine; (k) TMAOH: tetramethylammonium hydroxide; (l) TPAOH: tetrapropyiammonium hydroxide; and (m) DEEA: 2-diethylaminoethanol.
Preparative Procedures FeTiAPOs may be prepared by forming a homogeneous reaction mixture containing reactive sources of iron, titanium, aluminum and phosphorous. The reaction mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
XAPO MOLECULAR SIEVES The XAPO molecular sieves of U.S. Serial No. 599,810, filed April 13, 1984, and U.S. Serial No. 902,020 filed September 2, 1986 have a three-dimensional microporous framework structure of MO2 n, AlO2- and PO2 + tetrahedral. oxide units, where "n" is 0, -1 or -2, and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (MxAlyPz)O2
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "M" represents at least one element from each of the classes of: 1) iron and titanium; and 2) cobalt, magnesium, manganese and zinc; "n" is 0, -1 or -2; "m" represents a molar amount of "R" present per mole of (MxAlyPz)O2 and has a value of zero (0) to about 0.3; and "x", "y" and "z" represent the mole fractions of "M", aluminum and phosphorus, respectively, present as tetrahedral oxides. The mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
A 0.02 0.60 0.38
B 0.02 0.38 0.60
C 0.39 0.01 0.60
D 0.98 0.01 0.01
E 0.39 0.60 0.01
In a preferred subclass of the XAPO molecular sieves the values of x, y and z are within the limiting compositional values or points as follows:
Mole Fraction
Point x y z a 0.02 0.60 0.38 b 0.02 0.38 0.60 c 0.39 0.01 0.60 d 0.60 0.01 0.39 e 0.60 0.39 0.01 f 0.39 0.60 0.01 XAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of "M", aluminum and phosphorous, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the XAPO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 2 hours to about 20 days, have been observed. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the XAPO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (MxAlyPz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6; "M" represents at least one element from each of the classes of: 1) iron and titanium; and 2) Cobalt, magnesium, manganese and zinc; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300; and "x", "y" and "z" represent the mole fractions of "M" (iron and/or titanium, and at least one of cobalt, magnesium, manganese and zinc), aluminum and phosphorous, respectively, and each has a value of at least 0.01, with the proviso that "x" has a value of at least 0.02.
In one embodiment the reaction mixture is selected such that the mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
F 0.02 0.60 0.38
G 0.02 0.38 0.60
H 0.39 0.01 0.60
I 0.98 0.01 0.Q1
J 0.39 0.60 . 0.01
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "x", "y" and "z" such that (x + y + z) = 1.00 mole.
XAPO molecular sieves are prepared as follows: Preparative Reagents XAPO compositions may be prepared by using numerous reagents. The preferred sources of elements "M" for preparing XAPOs are the same as those for preparing other APOs containing the same elements, as described above and below. Other reagents which may be employed to prepare XAPOs include:
(a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous phosphoric acid;
(d) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(e) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(f) Pr2NH: di-n-propylamine, (C3H7)2NH;
(g) Pr3N: tri-n-propylamine, (C3H7)3N
(h) Quin: Quinuclidine, (C7H13N) ;
(i) MQuin: Methyl Quinuclidine hydroxide,
(C7H13 NCH3OH); (j) C-hex: cyclohexylamine; (k) TMAOH: tetramethylammonium hydroxide (l) TPAOH: tetrapropylammonium hydroxide; and (m) DEEA: 2-diethylaminoethanol. Preparative Procedures XAPOs may be prepared by forming a homogenous reaction mixture containing reactive sources of element "M", aluminum and phosphorous. The reaction mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature ( 150 °C or 200 °C) for a time or placed in lined screw top bottles for digestion.at 100°C. Digestions are typically carried out under autogenous pressure.
MIXED-ELEMENT APO MOLECULAR SIEVES The mixed element APO molecular sieves of U.S. Serial No. 599,978, filed April 13, 1984, and U.S. Serial No. 846,088 filed March 31, 1986 have a framework structure of MO2 n, AIO2- and PO2 + tetrahedral units, wherein MO2 n represents. at least two different elements present as tetrahedral units "MO2 n" with charge "n", where "n" may be -3, -2, -1, or 0 or +1. One of the elements "M" is selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium, while a second one of the elements "M" is selected from the group consisting of cobalt, iron, magnesium, manganese,, titanium and zinc. Preferably, "M" is a mixture of lithium and magnesium. The mixed-element molecular sieves have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (MxAlyPz)O2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (MxAlyPz)O2 and has a value of zero to about 0.3, but is preferably not greater than 0.15; and "x", "y" and "z" represent the mole fractions of the elements "M" (i.e. "x" is the total of the mole fractions of the two or more elements "M"), aluminum and phosphorous, respectively, present as tetrahedral oxides. The mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
A 0.02 0.60 0.38
B 0.02 0.38 0.60
C 0.39 0.01 0.60
D 0.98 0.01 0.01
E 0.39 0.60 0.01
In a preferred subclass of the mixed-element APO molecular sieves the values of x, y and z are within the limiting compositional values or points as follows:
Mole Fraction
Point x y z a 0.02 0.60 0.38 b 0.02 0.38 0.60 c 0 .39 0 . 01 0 . 60 d 0 .60 0 . 01 0 .39 e 0 . 60 0 . 39 0 . 01 f 0 .39 0 . 60 0 . 01
An especially preferred subclass of the mixed-element APO molecular sieves are those in which the value of x is not greater than about 0.10.
A second group (FCAPO's) of mixed element APO molecular sieves are described in U.S. Patent No. 4,686,093 issued August 11, 1987 (incorporated herein by reference).
The mixed-element APO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of the elements "M", aluminum and phosphorous, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature between about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the APO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 2 hours to about 20 days, and preferably about 12 hours to about 5 days, have been observed. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the mixed-element APO compositions, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
aR : (MxAlyPz)O2 : bH2O
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and most preferably not more than 0.5; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably not greater than about 20, and most desirably not more than about 10; and "x", "y" and "z" represent the mole fractions of "M", aluminum and phosphorous, respectively, "y" and "z" each having a value of at least 0.01 and "x" having a value of at least 0.02, with each element "M" having a mole fraction of at least 0.01.
In one embodiment the reaction mixture is selected such that the mole fractions "x", "y" and "z" are generally defined as being within the limiting compositional values or points as follows:
Mole Fraction
Point x y z
F 0.02 0.60 0.38 G 0 . 02 0 . 38 0 . 60
H 0 . 39 0 . 01 0 .60
I 0 . 98 0 . 01 0 . 01
J 0 . 39 0 . 60 0 . 01
Preferred reaction mixtures are those containing not. more than about 0.2 moles of the metals "M" per mole of phosphorous.
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "x", "y" and "z" such that (x + y + z) = 1.00 mole.
Since the exact nature of the mixed-element APO molecular sieves is not clearly understood at present, although all are believed to contain MO2 tetrahedra in the three-dimensional microporous crystal framework structure, it is advantageous to characterize the mixed-element APO molecular sieves by means of their chemical composition. This is due to the low level of the elements "M" present in certain of the mixed-element APO molecular sieves prepared to date which makes it difficult to ascertain the exact nature of the interaction between the metals "M", aluminum and phosphorus. As a result, although it is believed that MO2 tetrahedra are substituted isomorphously for AlO2 or PO2 tetrahedra, it is appropriate to characterize certain mixed-element APO compositions by reference to their chemical composition in terms of the mole ratios of oxides.
Molecular sieves containing the metals "M", aluminum and phosphorous as framework tetrahedral oxide units are prepared as follows: Preparative Reagents Mixed-element APO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare mixed-element APOs include:
(a) aluminum isopropoxide;
(b) pseudoboehmite or other aluminum oxide;
(c) H3PO4: 85 weight percent aqueous phosphoric acid;
(d) lithium phosphate or magnesium hydroxide or appropriate salts of the other elements "M", as described above;
(e) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide;
(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide;
(g) Pr2NH: di-n-propylamine, (C3H?)2NH;
(h) Pr3N: tri-n-propylamine,
(C3H7)3N (i) Quin: Quinuclidine, (C7H13N) ; (j) MQuin: Methyl Quinuclidine hydroxide,
(C7H13 NCH3OH) ; (k) C-hex: eyelohexylamine; (l) TMAOH: tetramethylammonium hydroxide (m) TPAOH: tetrapropylammonium hydroxide; and (n) DEEA: 2-diethylaminoethanol. Preparative Procedures Mixed element APOs may be prepared by forming a starting reaction mixture by mixing aluminum oxide, magnesium hydroxide, lithium phosphate (or the corresponding salts of the other elements "M"). To this mixture the phosphoric acid is added. The resultant mixture is then blended until a homogeneous mixture is observed. To this mixture the templating agent is added and the resulting mixture blended until a homogeneous mixture is. observed.
The reaction mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogeneous pressure.
SILICOALUMINOPHOSPHATE MOLECULAR SIEVES The preferred NZMSs, to date, are the silicoaluminophosphate molecular sieves described in U.S. Patent No. 4,440,871 (incorporated herein by reference), and U.S. Serial No. 575,745, filed January 31, 1984.
The processes of the present invention may be conducted with the amine starting material(s) in the liquid phase. However, in view of the temperatures which are needed in practice to carry out the processes of the present invention at an economical rate, the processes of the present invention can be operated as a heterogeneous, gas phase reaction with the amine starting material(s) in the gaseous phase, since gas phase processes can be run at higher temperatures under relatively moderate pressures (typically of the order of a few atmospheres) using comparatively inexpensive equipment.
In such gas phase processes, the amine starting material(s) may be mixed with a carrier such as nitrogen, ammonia or steam (water), while being contacted with the molecular sieve; the carrier should of course be chosen so that it does not prevent the preparation of the desired products. While the use of such a carrier may be beneficial, the processes of the present invention can be operated using pure amine starting material(s) as the gaseous feed. The degree of dilution of the starting material with such a carrier may vary considerably depending upon any process constraints restricting the use of the carrier. For example, in commercial production, the use of very large quantities of. some carriers may be disadvantageous due to the cost of pumping large volumes of the carrier and increased difficulty in isolating the product, which increase the energy costs of the process. If the processes of the present invention are to be carried out using a carrier, in general it is recommended that the amine starting material(s) constitute from about 1 to about 95, and preferably about 9 to about 30, mole percent of the starting material/carrier feed. Increasing the dilution of the starting material with a carrier such as water may tend to increase the selectivity of the reaction to the particular products desired. An embodiment of this invention involves adding water or steam to the feed or reaction to selectively produce triethylenediamine at enhanced reaction rates. Increasing the dilution of the amine starting material(s) with water can accelerate certain amine transformations and also increase the selectivity. of the reaction to particular products. For example, as demonstrated in the Examples hereinafter, the presence of steam can accelerate the piperazine to triethylenediamine reaction and increase the selectivity of the reaction to triethylenediamine.
Another embodiment of this invention involves conducting the amine transformations under oxidizing conditions to selectively produce certain amine products. For example, as demonstrated in the Examples hereinafter in regard to the reaction of aqueous piperazine in the presence of oxygen, increasing oxygen levels can increase the selectivity of the reaction to pyrazines. Suitable oxidizing agents for use in the processes of this invention include oxygen and air.
Selection of the temperature at which the processes of the present invention are to be conducted involves a compromise between selectivity to the desired product (s) and conversion of the amine starting material(s). It is recommended that the processes of the present invention be conducted at temperatures in the range of about 250°C to about 500°C; below this temperature range, the reaction tends to proceed too slowly, while at very high temperatures, the selectivity to the desired products decreases dramatically. At least for piperazine conversion, the preferred temperature range is from about 350°C to 425°C.
The processes of the present invention can .be run over a wide range of pressures ranging from atmospheric or subatmospheric pressures to 5000 psig. (6.9 MPa.) or more. However, since the use of very high pressures has not been observed to confer any significant advantages but increases equipment costs, the processes of the present invention may be carried out at a pressure of from about atmospheric pressure to about 1000 psig (about 7 MPa.).
The processes of the present invention can also be carried out over a wide range of weight hourly space velocities of the amine starting material(s). For example, weight hourly space velocities of from about 0.01 to about 50 or greater may be employed, with the preferred range of weight hourly space velocity being from about 0.1 to about 10, based on the amine starting material(s).
The processes of this invention can be carried out over a wide range of liquid hourly space velocities of the amine starting material(s). For example, liquid hourly space velocities of from about 0.01 to about 50 or greater may be employed, with the preferred range of liquid hourly space velocity being from about 0.1 to about 10, based on the amine starting material(s).
The processes of this invention can be carried out over a wide range of gas hourly space velocities of the amine starting material(s) and carrier. For example, gas hourly space velocities of from about 1 to about 5000 or greater may be employed, with the preferred range of gas hourly space velocity being from about 100 to about 3000, based on the amine starting material(s) and carrier.
The molecular sieve catalysts used in the processes of the present invention enable the reaction to be carried out at high conversions and selectivities. As illustrated in the Examples below, the processes of the present invention can be carried out at a conversion of from about 5% or less to about 50% or greater with selectivities to amine products, e.g., triethylenediamine, of 100%.
As with some reactions catalyzed by molecular sieves, the conversion achieved in the processes of the present invention may tend to fall as the time for which the molecular sieve catalyst has been used in the processes increases. If the molecular sieve catalysts become deactivated, then the deactivated catalyst can readily be regenerated by heating in air at an appropriate temperature (typically about 500°C) and for an appropriate period (typically one hour or more). It is one of the advantages of the processes of the present invention that at least some of the instant catalysts can be run for at least 40 hours of operation without the need for reactivation, whereas some of the prior art catalysts used for the same conversions rapidly deactivate.
The molecular sieves may be modified by depositing or impregnating the molecular sieve with cations, anions or salts so as to improve their efficacy as catalysts in the processes of the present invention. Techniques which may be employed to effect the deposition or impregnation of a molecular sieve are generally known in the art. Such techniques may involve such procedures as (1) impregnating the molecular sieve with a solution comprising a solvent or solubilizing agent of one or more such modifying materials in an amount sufficient to deposit the desired weight of such materials in the molecular sieve and/or (2) exchanging the molecular sieve with a solution containing the modifying material. The impregnation or deposition of the modifying materials may generally be accomplished by heating the molecular sieve at an elevated temperature to evaporate any liquid present to effect deposition or impregnation of the modifying material on to the interior and/or exterior surface of the molecular sieve, or by the exchange of cations present in the molecular sieve with cations that provide for the desired properties (provided of course that the molecular sieve is one having a significant ion-exchange capacity). Alternatively, the modifying material may be formed on the molecular sieve from a solution, an emulsion or a slurry containing the modifying material. Impregnation or exchange procedures are generally the preferred techniques because they utilize and introduce the modifying material more efficiently than other procedures such as coating procedures since a coating procedure is generally not able to effect substantial introduction of the modifying material on to the interior surfaces of the molecular sieve. In addition, coated materials are more generally susceptible to the loss of the modifying materials by abrasion.
Suitable modifying materials include alkali metals, alkaline earth metals, transition metals andthe salts thereof including inorganic and organic salts such as nitrates, halides, hydroxides, phosphates, sulfates and carboxylates. Other modifying materials generally employed in the art are also believed to be employable in the molecular sieves. An embodiment of this invention is the use of silica molecular sieves treated with phosphoric acid or phosphoric acid equivalents such as diammonium hydrogen phosphate in the processes described herein. The processes of this invention in which modified molecular sieves are used as cyclization catalysts can provide amine products having low linear/cyclic weight ratios.
These phosphorylated molecular sieves used in the processes of this invention can be prepared by conventional methods known in the art. For example, the particular molecular sieve can be treated with phosphoric acid or phosphoric acid equivalents such as diammonium hydrogen phosphate (DAHP) to provide a catalyst which is highly selective for cyclization and highly active. As used herein, the term "modified molecular sieves" refers to molecular sieves that are treated by depositing or impregnating the molecular sieves with cations, anions or salts so as to improve their efficacy as a catalyst in the processes of the present invention. In carrying out the processes of the present invention, the molecular sieves may be admixed (blended) or provided sequentially to other materials which may provide some property which is beneficial under process conditions, such as improved temperature resistance or improved catalyst life by minimization of coking, or which are simply inert under the process conditions used. Such materials may include synthetic or naturally- occurring substances as well as inorganic materials such as clays, silicas, aluminas, metal oxides and mixtures thereof. In addition, the molecular sieves may be formed with materials such as silica, alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-berylia, and silica-titania, as well as ternary compositions, such "as silica-alumina-thoria, silica-alumina- zirconia and clays present as binders. The relative proportions of the above materials and the molecular sieves may vary widely with the molecular sieve content ranging between about 1 and about 99 percent by weight of the composite. A preferred catalyst for use in this invention is Silicalite-SiO2 bonded or phosphorylated Silicalite-SiO2 bonded. Amorphous silica is a preferred binder for the pentasil crystalline structure molecular sieves.
The amine products produced by the processes of this invention can be separated by distillation. For example, the crude aqueous reaction product of piperazine and ethylenediamine to triethylenediamine can be subjected to a distillation-separation at atmospheric pressure at a 2:1 reflux ratio through an 11-ρlate Oldershaw distillation column. Evaluation of the distillate fractions shows that triethylenediamine can be separated readily and in reasonable purity from piperazine and ethylenediamine, and piperazine and ethylenediamine can be separated from a number of lower boiling byproducts and recycled. Reactive distillation may be useful in conducting the processes of this invention.
The processes of this invention may be carried out using, for example, a fixed bed reactor, a fluid bed reactor, or a slurry reactor. The optimum size and shape of the catalyst particle will depend on the type of reactor used. In general, for fluid bed reactors, a small, spherical catalyst particle is preferred for easy fluidization. With fixed bed reactors, larger catalyst particles are preferred so the back pressure within the reactor is kept reasonably low.
The processes of this invention can be conducted in a batch or continuous fashion. The reaction can be conducted in a single reaction zone or in a plurality of reaction zones, in series or in parallel or it may be conducted batchwise or continuously in an elongated tubular zone or series of such zones. The materials of construction employed should be inert to the reactants during the reaction and the fabrication of the equipment should be able to withstand the reaction temperatures and pressures. Means to introduce and/or adjust the quantity of reactions or ingredients introduced batchwise or continuously into the reaction zone during the course of the reaction can be conveniently utilized in the processes especially to maintain the desired molar ratio of the reactants. The processes may be conducted in either glass lined, stainless steel or similar type reaction equipment. The reaction zone may be fitted with one or more internal and/or external heat exchanger(s) in order to control undue temperature fluctuations, or to prevent any possible "runaway" reaction temperatures.
As used herein, the term "substituted" is contemplated to include all permissible substituents of amine compounds. Illustrative substituents include, for example, alkyl, aminoalkyl, hydroxyalkyl and the like in which the number of carbons can range from 1 to about 12 or more, preferably from 1 to about 4. The permissible substituents can be one or more and the same or different for appropriate amine compounds. This invention is not intended to be limited in any manner by the permissible substituents of amine compounds.
Many of the following Examples are provided to further illustrate the processes of the present invention, but are not limitative thereof. Unless otherwise specified, all parts, proportions etc. are by weight. The following abbreviations used in the Examples hereinafter have the indicated meanings: GHSV gas hourly space velocity
LHSV liquid hourly space velocity
WHSV weight hourly space velocity
PIP piperazine AEP N-(2-aminoethyl)piperazine
HEP N-(2-hydroxyethyl)piperazine
DETA diethylenetriamine
TETA triethylenetetraamine
AEEA aminoethylethanolamine
MEA monoe.thanolamine
EDA ethylenediamine
DAHP diammonium hydrogen phosphate
TEDA triethylenediamine or
1,4-diazabicyclo[2.2.2]octane
Methyl TEDA 2-methyl-triethylenediamine or
2-methyl-1,4-diazabicyclo[2.2.2]- octane
MIPA isopropanolamine (both isomers) DABCO 1,4-diazabicyclo[2.2.2]octane or triethylenediamine
Methyl DABCO 2-methyl-1,4-diazabicyclo-
[2.2.2]octane or
2-methyl-triethylenediamine
ESCA electron spectroscopy for chemical analysis
EDTA ethylenediaminetetracetic acid TAEA tris(2-aminoethyl) amine at. % atom percent
Examples
The molecular sieve catalysts used in the Examples hereinafter are conventional materials prepared by conventional methods. Typically the organic template was removed.
Untreated molecular sieve catalysts (powder) used in the Examples hereinafter were loaded into a microreactor or plug-flow reactor described below and calcined under nitrogen at a temperature of about 400°C for a period of 1-2 hours before the reaction. When any of the molecular sieve catalysts were used for more than one run, it was regenerated by calcining at a temperature of 500°C in air for a period of at least 2 hours.
Treated molecular sieve catalysts (diammonium hydrogen phosphate) used in the Examples hereinafter were prepared by refluxing a molecular sieve powder in a saturated solution of diammonium hydrogen phosphate for a period of 4 hours. The solids were collected by filtration or centrifugation and were washed with 25 milliliter portions of distilled water until the water wash was neutral. The solids were then dried at a temperature of 100°C for a period of about 1 hour and then calcined overnight under air at a temperature of 600°C.
The catalytic reactions for Examples 1-28 were conducted in a microreactor consisting of a 3/8 inch (9 mm.) diameter stainless steel tube encased in a 1 inch (25 mm.) diameter sheath of stainless steel heated with an electric split furnace. Approximately 1 gram of catalyst as the powder was dispersed among about 5 grams of 20-30 U. S. mesh quartz chips and placed in the heated zone of the reactor. The reactor tube was disposed vertically with a downward flow of reactants and products. Connected to the inlet of the reactor were a source of nitrogen or ammonia carrier gas and a liquid feed line (reaction starting materials as a 15% or 30% solution in water or acetonitrile) connected to a high pressure liquid chromatography (HPLC) type solvent pump. For the feeds containing ammonia, the feed reservoir was a Hoke cylinder pressurized to .about 200 psi to keep the reactants liquid until introduced to the reactor. Immediately below the reactor was disposed a cold trap kept at 0°C in which products were collected. Gas chromatographic analysis of the reactor off gas down stream from the cold trap indicated that virtually all of the products and reactants were collected in the cold trap. The products of the reaction collected in the cold trap were analyzed by gas chromatography on a 12 foot by 1/8 inch (3658 by 3 mm.) column containing TERGITOL non-ionic TMN (a polyether liquid phase) and 3 percent sodium methylate on 60/80 Chromasorb W-NAW, or on a 10 foot by 1/8 inch (3048 by 3 mm.) column containing 8 percent TERGITOL non-ionic E68 and 2 percent potassium hydroxide.
The catalytic reactions for Examples 29-98 were conducted in a fixed bed, plug-flow reactor consisting of a 2.2 centimeter internal diameter, 80 centimeters long, stainless steel, electrically heated pipe reactor. The center portion of the reactor contained 100 milliliters of 1/16 inch stranded catalyst. The top 20 centimeters of the reactor was packed with 2 millimeter glass beads, the catalyst bed depth was about 30 centimeters and the 25 centimeter lower part of the reactor was also packed with 2 millimeter glass beads. Temperatures were measured through a sliding thermocouple inside a 1/16 inch well located axially in the reactor so that the center longitudinal temperatures could be monitored at any time and any place in the reactor. Prior to the reactor was a preheater-evaporator made of 20 feet by 1/4 inch stainless steel tubing coiled within an electric heater. The aqueous feed was metered in via a plunger pump. The product was condensed and trapped as described above for the microreactor. Reagent/products were in a down-flow mode. Analyses were carried out in a Hewlett-Packard 5890 gas chromatograph using a SPB-5, 30 meter capillary column and a fid detector.
Examples 1-12
These examples demonstrate the use of various DAHP treated molecular sieves as cyclization catalysts for the reaction of MEA and EDA to cyclic and acyclic amine products. The amine products produced using DAHP treated molecular sieves exhibit low linear/cyclic weight ratios.
The microreactor described above was charged with 1.0 gram of a catalyst identified in Table A below and heated to a temperature of 325°C. Nitrogen carrier gas was passed through the reactor at a GHSV of 840 at a pressure of 850 psi. MEA, EDA and ammonia (1:2:6 molar ratio respectively) were fed into the nitrogen stream at a WHSV of 2.0. Analysis of the products of the reaction showed a conversion and product distribution as set forth in Table A. Table A
1 2 3 4 5 6 7 8 9 10 11 12
LZ-10 LZ-10* LZ-227 LZ-227* AlPO4-5 AlPO4-5* SAPO-5 SAPO-5* Silicalite Silicalite* TASO-45 TASO-45
in (percent) 70 75 2 11 8 63 18 60 30 73 25 40 distribution ercent)
18 18 3 10 10 20 15 24 35 41 32 35 9 12 2 10 8 26 11 24 23 23 17 22 1 1 2 0 1 0 1 0 1 1 1 0 0 0 q 1 1 1 1 2 0 10 3 7 8 2 20 41 25 4 23 4 18 2 14 9 1 0 0 9 5 0 4 0 1 0 2 1 1 0 0 3 0 0 4 1 0 0 3 0
Amines 62 46 71 27 50 49 41 45 22 23 28 26 lic 0.36 0.06 2.86 2.52 1.50 0.09 1.10 0.10 0.32 0.03 0.36 0.16 ght)**
d with DAHP.
/cylic ratio (weight) = (DETA + TETA + AEEA)/(PIP + AEP + HEP + TEDA).
Examples 13 and 14
These examples demonstrate the use of DAHP treated Silicalite as a cyclization catalyst for the reaction of AEP to TEDA and also HEP to TEDA at desired selectivities and conversions.
The microreactor described above was charged with 1.0 gram of catalyst (Silicalite treated with DAHP) and heated to a temperature of 350°C for each example. Nitrogen carrier gas was passed through the reactor at a GHSV of 1800 at atmospheric pressure. Either AEP (Example 13) or HEP (Example 14) was fed as a 30 percent solution in acetonitrile into the nitrogen stream at a WHSV of 2.0. Analysis of the products of the reaction showed a conversion and product distribution as set forth in Table B below.
Table B
Examples 13 14
Conversion (percent) 40 40
Product Distribution (weight percent)
PIP 30 10
TEDA 60 80
Other Amines 10 10
Examples 15 and 16 These examples demonstrate the use of DAHP treated Silicalite as a cyclization catalyst for the reaction of PIP and MEA to TEDA at desired selectivities and conversions (MEA). The microreactor described above was charged with 1.0 gram of catalyst (Silicalite treated with DAHP) and heated to a temperature of 375°C (Example 15) or 400°C (Example 16). Nitrogen carrier gas was passed through the reactor at a GHSV of 500 at atmospheric pressure. PIP and MEA (2:1 molar ratio respectively) were fed as a 15 percent solution in water into the nitrogen stream at a WHSV of 10.0. Analysis of the products of the reaction showed a conversion and product distribution as set forth in Table C below.
Table C
Examples 15 16
Conversion (percent) 50 100
Product Distribution (weight percent)
TEDA 100 100
Examples 17 and 18
These examples demonstrate the use of DAHP treated Silicalite as a cyclization catalyst for the reaction of PIP and MIPA to TEDA/Methyl TEDA and also the reaction of PIP and propylene glycol to TEDA at desired selectivities and conversions. Propylene glycol did not react with PIP under the reaction conditions.
The microreactor described above was charged with 1.0 gram of catalyst (Silicalite treated with DAHP) and heated to a temperature of 350°C for each example. Nitrogen carrier gas was passed through the reactor at a GHSV of 500 at atmospheric pressure. PIP and MIPA (Example 17) or PIP and propylene glycol (Example 18) (2:1 molar ratio respectively) were fed as a 15 percent solution in water into the nitrogen stream at a WHSV of 10.0. Analysis of the products of the reaction showed a conversion and product distribution as set forth in Table D below.
Table D
Examples 17 18
Conversion (percent) 30 30
Product Distribution (weight percent)
TEDA 80 100
Methyl TEDA 20 0
Examples 19-22
These examples demonstrate the use of DAHP treated Silicalite as a cyclization catalyst for the reaction of PIP to TEDA, PIP and ethylene glycol to TEDA and MEA to TEDA at desired selectivities and conversions.
The microreactor described above was charged with 1.0 gram of catalyst (Silicalite treated with DAHP) and heated to a temperature of 350°C for each example. Nitrogen carrier gas was passed through the reactor at a GHSV of 500 at atmospheric pressure. The reactants (PIP as a 10 percent solution in acetonitrile for Example 19, PIP as a 10 percent solution in water for Example 20, PIP and ethylene glycol in a 2:1 molar ratio respectively for Example 21 and MEA alone for Example 22) were fed into the nitrogen stream at a WHSV of 10.0. Analysis of the products of the reaction showed a conversion and product distribution as set forth in Table E below.
Table E
Examples 19 20 21 22
Conversion (percent) 15 30 30 30
Product Distribution (weight percent)
PIP 0 0 0 25
TEDA 100 100 90 65
Other Amines 0 0 10 10
Examples 23-28 These examples demonstrate the use of various non-zeolitic molecular sieves as cyclization catalysts for the reaction of HEP to TEDA at desired selectivities and conversions.
A microreactor similar to that described above was charged with 1.0 gram of catalyst identified in Table F below and 3.0 grams of 20-40 U.S. mesh quartz chips and heated to a temperature set forth in Table F. Nitrogen carrier gas was passed through the reactor at a flow of 3 cc/minute at atmospheric pressure. HEP was fed as a 75 percent solution in water into the nitrogen stream at a rate of 2 cc/minute. Analysis of the products of the reaction showed a conversion and selectivity to TEDA as set forth in Table F.
The catalyst used in Example 26 was prepared by the following procedure. Strontium nitrate (20 grams) was dissolved in 40 milliliters of water and to that was added a solution of DAHP (3.6 grams) in 40 milliliters of water. The solid produced was filtered and the clear effluent (pH 4.17) was used to treat 20 grams of SAPO-5. As soon as the SAPO-5 was added the pH changed to 2.7. Ammonium hydroxide was added to bring the pH back to the pH of the original liquid. Thereafter, the solution was allowed to stand at room temperature with periodic addition of either ammonium hydroxide or of nitric acid to maintain pH 4.17. The exchanged SAPO-5 was then filtered, dried at 120°C and then dried further at 200°C. X-Ray analysis showed the SAPO-5 had retained its crystallinity. Elemental analysis gave the following results: Si: 4.93%, Al: 20.0%; P: 20.3% and Sr: 0.27%.
Table F
Examples 23 24 25 26 27 28
Catalyst SAPO-11 SAPO-5 SAPO-5 SrSAPO-5 MnAPO-5 AIPO4-5
Conversion (percent) 86 23 50 23 15 23
Temperature (°C) 372 353 370 352 351 346
Selectivity to TEDA 42 35 32 33 26 20 (percent)
Examples 29-39
These examples demonstrate the use of DAHP treated Silicalite as a cyclization catalyst for the reaction of PIP to cyclic and acyclic amine products,
The plug-flow reactor described above was charged with 100 milliliters of catalyst identified in Table G below and heated to a temperature of 350°C for each. example. The catalyst used in Examples 29 and 31-36 was Silicalite-SiO2 bonded obtained from Union Carbide Cooperation, Danbury, Connecticut, and the catalyst used in Examples 30 and 37-39 was DAHP treated Si lica lite-SiO2 bonded prepared in a manner similar to Catalyst B (see Examples 40-51). PIP as a 35 weight percent solution in water was fed into the reactor at a LHSV of 0.8 (relative to the total solution). Analysis of the products of the reaction showed a conversion and product distribution as set forth in Table G.
The activities of the catalysts used in Examples 29 and 30 are set forth in Table H below.
Figure imgf000186_0001
Table H
31 32 33 34 35 36 37 38
Silicalite Silicalite Silicalite Silicalite Silicalite Silicalite Silicalite* Silicalite* Silicalite* tream (hours) 44 100 140 168 212 256 96 134 137 istribution ercent)
22.3 20.3 16.1 16.8 18.3 17.3 18.8 18.7 18.9 y to 93.1 - - 92.0 - 97.5 92.2 cent)
i with DAHP.
Examples 40-51
These examples demonstrate the use of various modified molecular sieves as cyclization catalysts for the reacton of PIP to TEDA at desired selectivities and conversions.
The plug-flow reactor described above was charged with 100 milliliters of catalyst identified in Table I below and heated to a temperature of 350°C for each example. PIP as a 35 weight percent solution in water was fed into the reactor at a LHSV of 0.8 (relative to the total solution). Analysis of the products of the reaction showed a conversion and TEDA efficiency as set forth in Table I.
The catalysts used in Examples 40-51 were prepared according to the following procedures.
Catalyst A was base Silicalite-SiO2 bonded obtained from Union Carbide Corporation,
Danbury, Connecticut, and used as 1/16" strands. The BET-N, surface area was 359 m2/g (to 15 A, multipoint). The pore volume was 0.268 cm 3/gram and the surface area was 52.1 m2/gram (both by Hg intrusion).
Analyses:
ESCA (wt. %)
Bulk Powdered (wt.%) Pellet Pellet
Al 0.53 1.15 2.08
Na 0.18 0.26 0.68
Mg 330 (ppm) -- --
Catalyst B was prepared by immersing Catalyst A (73.8 grams; 100 milliliters) in 300 grams of a 5.0 wt. % aqueous DAHP solution at room temperature overnight. The liquid was drained off and the catalyst washed twice, rapidly with 75 milliliters each of distilled water. The catalyst was then heated to a temperature of 450°C for a period of 18 hours in air.
Analyses:
ESCA (wt%)
Powdered Bulk Pellet Pellet
P (at.%) 0.18 1.28 1.15
Catalyst C was prepared by refluxing Catalyst A (90 grams; ~100 milliliters) in 300 grams of a 10.7% aqueous DAHP solution for a period of 18 hours. The liquid was drained off and the solids washed twice, rapidly with 75 milliliters each of distilled water. The catalyst was then heated to a temperature of 450°C in air for a. period of 18 hours.
Analyses:
ESCA (wt%)
Powdered Bulk Pellet Pellet
P (at.%) 0.32 1.46 1.46
Catalyst D was prepared by immersing Silicalite--Al2O3 bonded, 1/16" strands (75.3 grams; 100 milliliters) obtained from Union Carbide Corporation, Danbury, Connecticut, in 74.1 grams of an aqueous 5% DAHP solution at room temperature overnight. The liquid was drained off and the solids washed twice with 75 milliliters each of distilled water followed by heating at a temperature of 450°C in air for a period of 18 hours.
Analyses:
ESCA (wt%)
Powdered Bulk. Pellet Pellet
P (at.%) 0.37 2.06 2.22
Catalyst E was prepared by immersing Catalyst A (77.6 grams; 110 milliliters) in a 7.4 wt. % aqueous DAHP solution at room temperature overnight. The liquid was drained off and the solids washed twice with 75 milliliters distilled water each, followed by heating at a temperature of 450°C in air for a period of 18 hours. The solids were immersed in 75 grams of a 13.3% aqueous Mg(NO3)2·6H2O solution overnight at room temperature followed by washing and heating as above.
Analyses:
ESCA (wt%)
Powdered Bulk Pellet Pellet
P (at. %) 0.48
Mg (at. %) 0.22 0.36 0.32
Catalyst F was prepared by extracting
Catalyst A (76.1 grams; 110 milliliters) three times with a ~10% aqueous EDTA-4Na+ 4 4 solution at at a temperature of 95°C for a period of 18 hours each. The solids were washed three times with 250 milliliters of distilled water each and then ion-exchanged with ~10% aqueous NH4NO3 three times at a temperature of 95°C for a period of 18 hours. The solids were rinsed with distilled water three times, 250 milliliters each, and heated at a temperature of 450°C in air for a period of 18 hours.
Analyses:
ESCA (wt%)
Powdered Bulk Pellet Pellet
Al (at.%) 0.42 1.6 0.8
Catalyst G was prepared by ion exchanging Catalyst A (82.9 grams; 110 milliliters) using a 5% aqueous NH4Cl solution at a temperature of 95°C overnight. The solids were washed and heated at a temperature of 450°C in air for a period of 18 hours. The solids were then immersed in 200 milliliters of 2.5% aqueous Ga(NO3)3~9H2O solution at a temperature of 95°C overnight. The liquors were drained off and the solids washed and heated at a temperature of 550°C.
Analyses:
ESCA (wt%)
Powdered
Bulk Pellet Pellet
Ga (at.%) 0.21 10.1 0.81
Al (at.%) 0.14 <0.2 <0.2
Na (ppm) 150 0.0 0.0
Catalyst H was prepared by soaking 74.4 grams of SAPO-11 as 1/16" Al2O3-bonded strands obtained from Union Carbide Corporation, Danbury, Connecticut in (100 milliliters) 75.1 grams of a 5% DAHP solution (aqueous) and left to stand at room temperature overnight. The liquid was drained off and the solids heated at a temperature of 450°C in air overnight.
Catalyst I was SAPO-4l-SiO2 bonded, 1/16" strands, obtained from Union Carbide Corporation, Danbury, Connecticut and used in unmodified form.
Catalyst J was about 250 milliliters of amorphous silica (Fuji-Davison, 5-10 mesh balls) obtained from W. R. Grace Chemical Company Cariact 10; lot number CA-30507; ~290 m2/gram surface area; 1.03 cm3/gram porosity (Hg) . This contained
0.01% Fe, 0.02% Al and 0.06% Na, 99.8% SiO2.
Catalyst K was prepared by adding 110 milliliters (46.3 grams) of amorphous silica as used in the preparation of Catalyst J to a solution of 5.8 grams of Al(NO3)3·9H2O in 50 milliliters of distilled water and soaked for a period of 4 hours at room temperature. The catalyst was dried and heated at a temperature of 450°C in air for a period of 18 hours.
Analyses:
ESCA (wt.%)
Powdered Pellet Pellet
Al 1.58 0.47
Bulk (at.%) Al 0.60
Na 0.03
Mg 0.01 Catalyst L was prepared by adding 110 milliliters (46.3 grams) of amorphous silica as used in the preparation of Catalyst J to a solution of 29.1 grams of Al(NO3)3·9H2O in 50 milliliters of distilled water and soaked for a period of 4 hours at room temperature. The catalyst was dried and heated at a temperature of 450º in air for a period of 18 hours.
Analyses:
ESCA (wt.%)
Powdered Pellet Pellet
Al 2.03 1. ,73
Na & K 0.0 0. ,0
Bulk (at.%)
Al 2.30 Na 0.02 Mg 0.01
T able I
Examples. 40 41 42 43 44 45
Catalyst A B C D E F
Catalyst Additive (weight percent)
Phosphorus -- 0.29 0.51 0.60 -- --
Magnesium -- -- -- -- 0.23 --
Aluminum (0.53) (0,53) (0,53) -- (0,53) 0.50
Conversion (percent) 20.5 19.0 14.7 18.6 15.8 5.9
Efficiency to TEDA (percent) 93.1 92.9 88.2 88.9 90.5 85.7
Table I (Cont,)
Examples 46 47 48 49 50 51
Catalyst G H I J K L
Catalyst Additive (weight percent)
Phosphorus -- -- -- -- -- --
Magnesium -- -- -- -- -- --
Aluminum -- -- -- ~200ppm 0.80 3. 1
Conversion (percent) 20 3.8 9.2 0 8.2 10.1
Effi ciency to
TEDA (percent) ≤90 74.8 83.8 -- 80.4 72.5
Examples 52-58
These examples demonstrate the use of DAHP treated Silicalite as a cyclization catalyst for the reaction of various amine starting materials to cyclic and acyclic amines at desired selectivities.
The plug-flow reactor described above was charged with 100 milliliters of catalyst (Silicalite treated with DAHP in a manner similar to the preparation of Catalyst B) and heated to a temperature of 350°C for each example. An amine starting material identified in Table J below was fed into the reactor at a LHSV of 0.8 (relative to the total solution). Analysis of the products of the reaction showed a product distribution as set forth in Table J.
Figure imgf000197_0001
Figure imgf000198_0001
Example 59
This example demonstrates the use of DAHP treated Silicalite as a cyclization catalyst for the reaction of MEA to cyclic and acyclic amines including TEDA and morpholine.
The plug-flow reactor described above was charged with 100 milliliters of catalyst (Silicalite treated with DAHP in a manner similar to the preparation of Catalyst B) and heated to a temperature of 350°C. MEA was fed into the reactor at a LHSV of 0.8 (relative to the total solution). Analysis of the products of the reaction showed a product distribution as set forth in Table K below.
Figure imgf000200_0001
Examples 60-63
These examples demonstrate the use of DAHP treated Silicalite as a cyclization catalyst for the reaction of aqueous PIP to cyclic and acyclic amines in the presence of oxygen. The use of an oxidizing atmosphere can enhance the production of pyrazines.
The plug-flow reactor described above was charged with 100 milliliters of catalyst (silicalite treated with DAHP in a manner similar to the preparation of Catalyst B) and heated to a temperature of 350°C for each example. PIP as a 35 weight percent solution in water was fed into the reactor at a LHSV of 0.8 (relative to the total solution). Oxygen was also fed into the reactor in an amount indicated in Table L below. Analysis of the products of the reaction showed a product distribution as set forth in Table L.
Figure imgf000202_0001
Figure imgf000203_0001
Figure imgf000204_0001
Figure imgf000205_0001
Examples 64-65 These examples demonstrate the use of Silicalite as a cyclization catalyst for the reaction of PIP and EDA to TEDA at desired selectivities. The co-feeding of EDA enhances the overall reaction rate to TEDA.
The plug-flow reactor described above was charged with 100 milliliters of catalyst (Silicalite-SiO2 bonded obtained from Union Carbide Corporation, Danbury, Connecticut) and heated to a temperature of 350°C for each example. PIP as a 35 weight percent solution in water and EDA (Example 65) were fed into the reactor at a LHSV of 0.8 (relative to the total solution). Analysis of the products of the reaction showed a conversion and product distribution as set forth in Table M below.
Figure imgf000207_0001
Examples 66-70 These examples demonstrate isothermal kinetics of the PIP to TEDA process using Silicalite as the cyclization catalyst.
The plug-flow reactor described above was charged with 100 milliliters of catalyst (Silicalite-SiO2 bonded obtained from Union Carbide Corporation, Danbury, Connecticut) and heated to a temperature of 350°C for each example. PIP (35:65 weight ratio of PIP:water) was fed into the reactor at a LHSV of 0.8 (relative to the total solution). Analysis of the products and kinetics of the reaction showed the results given in Table N below.
Table N
Examples 66 67 68 69 70
Product Rate* 20.7 41.5 75.2 116.8 147.5
(grams/hour)
TEDA (wt.%)** 45.4 27.7 14.3 10.8 7.8
PIP (wt.%)** 50.0 70.3 83,6 88.5 91.4
Other Amines 4.6 2.0 2.1 0.66 0,74
(wt.%)
C2 Equivalent Feed***
C2 Equivalent Product 1.034 1.004 0.9865 0.9780 0.9748
W/F (hr-1)**** 102.1 45.7 25.3 16.3 12.9
*Total aqueous product. * *Anhydrous basis. *** Measure of reaction efficiency, e.g., ratio of C2 equivalents in feed versus C2 equivalents in product. ****W = weight of catalyst (grams); F=reagent flow rate (moles/hour); unit = hour. A low W/F is indicative of a high flow rate, fast pumping, etc. F is expressed in mole of PIP + mole of water (not combined weight units).
Examples 71-76
These examples demonstrate the effect of reaction temperature on the PIP to TEDA process using Silicalite as the cyclization catalyst.
The plug-flow reactor described above was charged with 100 milliliters of catalyst (Silicalite-SiO2 bonded obtained from Union Carbide Corporation, Danbury, Connecticut) and heated to a temperature set forth in Table O below. PIP (35:65 weight ratio of PIP:water) was fed into the reactor at a LHSV of 0.8 (relative to the total solution). Analysis of the products of the reaction showed the results given in Table O.
Table O
Examples 71 72 73 74 75 76
Temperature (°C) 320 346 350 360 380 400 PIP (wt. %) 91.4 83.2 81.4 75.1 64.0 51.8 TEDA (wt. %) 7.66 15.1 17.3 22.7 31.3 39.2 Other Amines (wt. %) 0.9 1.7 2.3 2.2 4.7 9.0 k1 (hr-1)* 0.0288 0.0589 0.0660 0.0918 0.143 0.211
*innoo/% PTP)
W/F = k1 = first order rate constant. See Table N for W/F explanation.
Examples 77-82
These examples demonstrate the effect of aqueous PIP concentration on the PIP to TEDA process using Silicalite as the cyclization catalyst. The presence of water or steam can accelerate the PIP to TEDA transformation.
The plug-flow reactor described above was charged with 100 milliliters of catalyst (Silicalite-SiO2 bonded obtained from Union Carbide Corporation, Danbury, Connecticut) and heated to a temperature of 350°C for each example. Various aqueous PIP solutions having PIP:water weight ratios set forth in Table P below were fed into the reactor at a LHSV of 0.8 (relative to the total solution). Analysis of the products of the reaction showed the results given in Table P.
Table P
Examples 77 78 79 80 81 82
Feed Rate 80 147.5 77.6 36.0 17.1 18.8
(grams/hour)
Feed Reagent (wt.%)
PIP 65 35 35 17.5 8.75 8.75
Water 35 65 65 82.5 91.25 91.25J
Product Distribution (wt. %)
PIP 87.9 89.9 81.0 56.4 23.9 28.5
TEDA 10.7 9.33 16.8 40.6 70.4 68.9
Other Amines 1.4 0.8 2.2 3.6 5.7 2.6
W/F* 35.4 12.9 24.5 44.3 85.0 78.2 k1 (hr-1)** 0.0036 0.0083 0.0086 0.0129 0.0168 0.0161
"See Table N for explanation. **See Table 0 for explanation.
Examples 83-93 These examples demonstrate the use of Silicalite as a cyclization catalyst for the reaction of various aqueous alkylenediamines (substituted and unsubstituted) to cyclic and acyclic amine products.
The plug-flow reactor described above was charged with 100 milliliters of catalyst (Silicalite-SiO2 bonded obtained from Union Carbide Corporation, Danbury, Connecticut) and heated to a temperature indicated in Tables Q, R, S T, U, V, W, X and Y below for each example. Various aqueous alkylenediamine solutions (35:65 weight ratio of alkylenediamine:water) were fed into the reactor at a LHSV of 0.8 (relative to the total solution). Analysis of the products of the reaction showed a product distribution as set forth in Tables Q, R, S, T, U, V, W, X and Y.
Figure imgf000215_0001
Figure imgf000216_0001
Figure imgf000217_0001
Figure imgf000218_0001
Figure imgf000219_0001
Figure imgf000220_0001
Figure imgf000221_0001
220
Figure imgf000222_0001
Figure imgf000223_0001
Example 94 This example demonstrates the use of Silicalite as a cyclization catalyst for the reaction of aqueous 3-amino-l-propanol to cyclic and acyclic amine products.
The plug-flow reactor described above was charged with 100 milliliters of catalyst (Silicalite-SiO2 bonded obtained from Union Carbide Corporation, Danbury, Connecticut) and heated to a temperature indicated in Table Z below. 3-amino-1-propanol as a 35 weight percent solution in water was fed into the reactor at a LHSV of 0.8 (relative to the total solution). Analysis of the products of the reaction showed a product distribution as set forth in Table Z.
Figure imgf000225_0001
Examples 95-98 These examples demonstrate the use of Silicalite as a cyclization catalyst for the reaction of various amine starting materials with aqueous PIP or EDA to cyclic and acyclic amine products.
The plug-flow reactor described above was charged with 100 milliliters of catalyst ( Si licalite-SiO2 bonded obtained from Union Carbide Corportion, Danbury, Connecticut ) and heated to a temperature indicated in Tables AA and BB below for each example. Various amine starting materials with PIP or EDA at weight ratios indicated in Tables AA and BB were fed into the reactor at a LHSV of 0.8 (relative to the total solution). Analysis of the products of the reaction showed a product distribution as set forth in Tables AA and BB.
Figure imgf000227_0001
Figure imgf000228_0001
Although the invention has been illustrated by many of the preceding examples, it is not to be construed as being limited thereby; but rather, the invention encompasses the generic area as hereinbefore disclosed. Various modifications and embodiments can be made without departing from the spirit and scope thereof.

Claims

Claims
1. A process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting two or more amine starting materials with one or more molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves, the contacting of the two or more amine starting materials with the one or more molecular sieves being effected under conditions effective to convert at least one of the amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
2. The process of claim 1 wherein the two or more amine starting materials are selected from substituted and unsubstituted cyclic amines, acyclic amines, alkylenediamines, alkanolamines, alkylamines and polyalkylene polyamines.
3. The process of claim 1 wherein the two or more amine starting materials are selected from piperazine, ethylenediamine, monoethanolamine, isopropanolamine, diisopropanolamine, aminoethylethanolamine, N-(2-hydroxyethyl)piperazine,
N-(2-aminoethyl) piperazine, diethanolamine, triethanolamine, tris(2-aminoethyl)amine, morpholine, diethylenetriamine and triethylenetetraamine.
4. The process of claim 1 wherein the two or more amine starting materials are selected from piperazine, ethylenediamine, monoethanolamine, N-(2- aminoethyl)piperazine and N-(2-hydroxyethyl)piperazine.
5. The process of claim 1 wherein the two or more amine starting materials include piperazine and an alkylenediamine.
6. The process of claim 1 wherein the two or more amine starting materials include piperazine and ethylenediamine.
7. The process of claim 1 wherein the two or more amine starting materials are selected from piperazine, ethylenediamine and isopropanolamine.
8. The process of claim 1 which further comprises contacting two or more amine starting materials and optionally one or more non-amine starting materials with one or more molecular sieves.
9. The process of claim 8 wherein the one or more non-amine starting materials include diols.
10. The process of claim 8 wherein the one or more non-amine starting materials include ethylene glycol and propylene glycol.
11. The process of claim 1 wherein at least one of the amine starting materials is converted into triethylenediamine and/or one or more of pyrazine, substituted pyrazines, pyridine, substituted pyridines, piperidine, substituted piperidines, piperazine, substituted piperazines, aminoethylethanolamine, diethanolamine, ethylenediamine, allylamines, substituted triethylenediamines, morpholine and substituted morpholines.
12. The process of claim 1 wherein at least one of the amine starting materials is converted into triethylenediamine and/or one or more of pyrazine or substituted pyrazines.
13. The process of claim 1 wherein at least one of the amine starting materials is converted into triethylenediamine and/or one or more substituted triethylenediamines.
14. The process of claim 1 wherein at least one of the amine starting materials is converted into triethylenediamine or 1,4-diazabicyclo[2.2.2]octane (DABCO) and/or 2-methyl-triethylenediamine or 2-methyl-1,4-diazabicyclo[2.2.2] octane (methyl DABCO).
15. The process of claim 1 wherein the molecular sieve comprises a silica molecular sieve or mixtures thereof.
16. The process of claim 1 wherein the molecular sieve comprises a modified silica molecular sieve or mixtures thereof.
17. The process of claim 15 wherein the silica molecular sieve is selected from Silicalite, Silicalite II, fluoride Silicalite and mixtures thereof.
18. The process of claim 15 wherein the silica molecular sieve is Silicalite or modified Silicalite.
19. The process of claim 1 wherein the molecular sieve comprises a non-zeolitic molecular sieve or mixtures thereof.
20. The process of claim 1 wherein the molecular sieve comprises a modified non-zeolitic molecular sieve or mixtures thereof.
21. The process of claim 19 wherein the non-zeolitic molecular sieve has an empirical chemical composition on an anhydrous basis expressed by the formula I:
(I) mR(QwAlxPySiz)O2
where "Q" represents:
(a) at least one element present as a framework oxide unit "QO2 n" with charge "n" where "n" may be -3, -2, -1, 0 or +1; or
(b) an element having:
(i) a mean "T-O" distance in tetrahedral oxide structures between about 1.51 Angstroms and about 2.06 Angstroms,
(ii) a cation electronegativity between about 125 kcal/gm-atom to about 310 kcal/gm-atom, and (iii) the capability of forming stable Q-O-P, Q-O-Al or Q-O-Q bonds in crystalline three dimensional oxide structures having a "Q-O" bond dissociation energy greater than about 59 kcal/gm-atom at 298°K; "R" represents at least one organic templating agent present in the intracrystalline pore system;
"m" represents the molar amount of "R" present per mole of (QwAlxPySiz)O2 and has a value from zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of QO2 n, AlO2-, PO2 +, SiO2, respectfully, present as framework oxide units; and the mole fractions of "Q", aluminum, phosphorus and silicon, respectively, present as framework oxides said mole fractions being within the following limiting compositional values: w is equal to 1 to 98 mole percent; y is equal to 1 to 99 mole percent; x is equal to 1 to 99 mole percent; and z is equal to 0 to 98 mole percent.
22. The process of claim 19 wherein the non-zeolitic molecular sieve is selected from AlPO4, SAPO, MeAPO, MeAPSO, ELAPO and ELAPSO molecular sieves and mixtures thereof.
23. The process of claim 1 wherein the molecular sieve comprises a zeolitic molecular sieve or mixtures thereof.
24. The process of claim 1 wherein the molecular sieve comprises a modified zeolitic molecular sieve or mixtures thereof.
25. The process of claim 23 wherein the zeolitic molecular sieve is selected from A-type zeolitic molecular sieves, X-type zeolitic molecular sieves, Y-type zeolitic molecular sieves, L-type zeolitic molecular sieves, mordenite, LZ-10, LZ-210, LZ-211, LZ-212, LZ-227, omega zeolitic molecular sieves, LZ-202, LZ-105 and mixtures thereof.
26. The process of claim 23 wherein the zeolitic molecular sieve is selected from ZSM-5, ZSM-11, ZSM-12, ZSM-20, ZSM-34, omega zeolite, beta zeolite and mixtures thereof.
27. The process of claim 1 which is carried out at a temperature of about 250°C to about 500°C.
28. The process of claim 27 which is carried out at a temperature of about 350°C to about 425°C.
29. The process of claim 1 which is carried out at a pressure of from about atmospheric to about 5000 psig.
30. The process of claim 29 which is carried out at a pressure of from about atmospheric to about 1000 psig.
31. The process of claim 1 wherein the two or more amine starting materials are in the gaseous phase while being contacted with the one or more molecular sieves.
32. The process of claim 31 wherein the two or more amine starting materials are mixed with a carrier while being contacted with the one or more molecular sieves.
33. The process of claim 32 wherein the carrier is nitrogen, ammonia or steam.
34. The process of claim 1 wherein the contacting of the two or more amine starting materials with the one or more molecular sieves occurs under oxidizing conditions.
35. The process of claim 1 wherein the contacting of the two or more amine starting materials with the one or more molecular sieves occurs in the presence of water or steam.
36. The process of claim 32 wherein the two or more amine starting materials comprise from about 1 to about 95 mole percent of the total feed of starting material and carrier.
37. The process of claim 36 wherein the two or more amine starting materials comprise from about 9 to about 30 mole percent of the total feed of starting material and carrier.
38. A process for the conversion of piperazine and ethylenediamine to at least one of triethylenedi amine , pyrazine , substituted pyrazines , aminoethylethanolamine, diethanolamine, substituted triethylenediamines, morpholine and substituted morpholines, which process comprises contacting the piperazine and ethylenediamine with one or more molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves, the contacting of the piperazine and ethylenediamine with the one or more molecular sieves being effected under conditions effective to convert the piperazine into at least one of said products.
39. A process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more modified molecular sieves selected from (a) modified silica molecular sieves, (b) modified non-zeolitic molecular sieves, and (c) modified zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more modified molecular sieves being effected under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
40. The process of claim 39 wherein the one or more amine starting materials are selected from substituted and unsubstituted cyclic amines, acyclic amines, alkylenediamines, alkanolamines, alkylamines and polyalkylene polyamines.
41. The process of claim 39 wherein the one or more amiήe starting materials are selected from piperazine, ethylenediamine, monoethanolamine, isopropanolamine, diisopropanolamine, aminoethylethanolamine, N-(2-hydroxyethyl)piperazine, N-(2-aminoethyl)piperazine, diethanolamine, triethanolamine, tri s (2-aminoethyl) amine, morpholine, diethylenetriamine and triethylenetetraamine.
42. The process of claim 39 wherein the one or more amine starting materials are selected from piperazine, ethylenediamine, monoethanolamine, N-(2-aminoethyl) piperazine and N-(2-hydroxyethyl)-piperazine.
43. The process of claim 39 wherein the one or more amine starting materials include piperazine and an alkylenediamine.
44. The process of claim 39 wherein the one or more amine starting materials include piperazine and ethylenediamine.
45. The process of claim 39 wherein the one or more amine starting materials are selected from piperazine, ethylenediamine and isopropanolamine.
46. The process of claim 39 which further comprises contacting one or more amine starting materials and optionally one or more non-amine starting materials with one or more modified molecular sieves.
47. The process of claim 46 wherein the one or more non-amine starting materials include diols.
48. The process of claim 46 wherein the one or more non-amine starting materials include ethylene glycol and propylene glycol.
49. The process of claim 39 wherein at least one of the amine starting materials is converted into triethylenediamine and/or one or more of pyrazine, substituted pyrazines, pyridine, substituted pyridines, piperidine, substituted piperidines, piperazine, substituted piperazines, aminoethylethanolamine, diethanolamine, ethylenediamine, allylamines, substituted triethylenediamines, morpholine and substituted morpholines.
50. The process of claim 39 wherein at least one of the amine starting materials is converted into triethylenediamine and/or one or more of pyrazine or substituted pyrazines.
51. The process of claim 39 wherein at least one of the amine starting materials is converted into triethylenediamine and/or one or more substituted triethylenediamines.
52. The process of claim 39 wherein at least one of the amine starting materials is converted into triethylenediamine or 1,4-diazabicyclo[2.2.2]octane (DABCO) and/or 2-methyl-triethylenediamine or 2-methyl-1,4-diazabicyclo-[2.2.2]octane (methyl DABCO).
53. The process of claim 39 wherein the modified molecular sieve comprises a modified silica molecular sieve or mixtures thereof.
54. The process of claim 53 wherein the modified silica molecular sieve is selected from modified Silicalite, Silicalite II, fluoride Silicalite and mixtures thereof.
55. The process of claim 53 wherein the modified silica molecular sieve is modified Silicalite.
56. The process of claim 53 wherein the modified silica molecular sieve is phosphorylated Silicalite.
57. The process of claim 39 wherein the modified molecular sieve comprises a modified non-zeolitic molecular sieve or mixtures thereof.
58. The process of claim 57 wherein the modified non-zeolitic molecular sieve has an empirical chemical composition on an anhydrous basis expressed by the formula I:
(I) mR(QwAlxPySiz)O2
where "Q" represents: (a) at least one element present as a framework oxide unit "QO2 n" with charge "n" where "n" may be -3, -2, -1, 0 or +1; or
(b) an element having:
(i) a mean "T-O" distance in tetrahedral oxide structures between about 1.51 Angstroms and about 2.06 Angstroms,
(ii) a cation electronegativity between about 125 kcal/gm-atom to about 310 kcal/gm-atom, and
(iii) the capability of forming stable
Q-O-P, Q-O-Al or Q-O-Q bonds in crystalline three dimensional oxide structures having a
"Q-O" bond dissociation energy greater than about 59 kcal/gm-atom at 298°K;
"R" represents at least one organic templating agent present in the intracrystalline pore system;
"m" represents the molar amount of "R" present per mole of (QwAlxPySiz)O2 and has a value from zero to about 0.3; and
"w", "x", "y" and "z" represent the mole fractions of QO2 n, AIO2-, PO2 +, SiO2, respectfully, present as framework oxide units; and the mole fractions of "Q", aluminum, phosphorus and silicon, respectively, present as framework oxides said mole fractions being within the following limiting compositional values: w is equal to 1 to 98 mole percent; y is equal to 1 to 99 mole percent; x is equal to 1 to 99 mole percent; and z is equal to 0 to 98 mole percent.
59. The process of claim 57 wherein the modified non-zeolitic molecular sieve is selected from modified AlPO4, SAPO, MeAPO, MeAPSO, ELAPO and ELAPSO molecular sieves and mixtures thereof.
60. The process of claim 57 wherein the modified non-zeolitic molecular sieve is phosphorylated SAPO.
61. The process of claim 39 wherein the modified molecular sieve comprises a modified zeolitic molecular sieve or mixtures thereof.
62. The process of claim 61 wherein the modified zeolitic molecular sieve is selected from modified A-type zeolitic molecular sieves, X-type zeolitic molecular sieves, Y-type zeolitic molecular sieves, L-type zeolitic molecular sieves, mordenite, LZ-10, LZ-210, LZ-211, LZ-212, LZ-227, omega zeolitic molecular sieves, LZ-202, LZ-105 and mixtures thereof.
63. The process of claim 61 wherein the modified zeolitic molecular sieve is selected from modified ZSM-5, ZSM-11, ZSM-12, ZSM-20, ZSM-34, omega zeolite, beta zeolite and mixtures thereof.
64. The process of claim 61 wherein the modified molecular sieve is phosphorylated ZSM-5.
65. The process of claim 39 which is carried out at a temperature of about 250°C to about 500°C.
66. The process of claim 65 which is carried out at a temperature of about 350°C to about 425°C.
67. The process of claim 39 which is carried out at a pressure of from about atmospheric to about 5000 psig.
68. The process of claim 67 which is carried out at a pressure of from about atmospheric to about 1000 psig.
69. The process of claim 39 wherein the one or more amine starting materials are in the gaseous phase while being contacted with the one or more modified molecular sieves.
70. The process of claim 69 wherein the one or more amine starting materials are mixed with a carrier while being contacted with the one or more modified molecular sieves.
71. The process of claim 70 wherein the carrier is nitrogen, ammonia or steam.
72. The process of claim 39 wherein the contacting of the one or more amine starting materials with the one or more modified molecular sieves occurs under oxidizing conditions.
73. The process of claim 39 wherein the contacting of the one or more amine starting materials with the one or more modified molecular sieves occurs in the presence of water or steam.
74. The process of claim 70 wherein the one or more amine starting matetials comprise from about 1 to about 95 mole percent of the total feed of starting material and carrier.
75. The process of claim 74 wherein the one or more amine starting materials comprise from about 9 to about.30 mole percent of the total feed of starting material and carrier.
76. A process for the conversion of piperazine to at least one of triethylenediamine, pyrazine, substituted pyrazines, aminoethylethanolamine, diethanolamine, substituted triethylenediamines, morpholine and substituted morpholines, which process comprises contacting the piperazine with one or more modified molecular sieves selected from (a) modified silica molecular sieves, (b) modified non-zeolitic molecular sieves, and (c) modified zeolitic molecular sieves, the. contacting of the piperazine with the one or more modified molecular sieves being effected under conditions effective to convert the piperazine into at least one of said products.
77. A process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more non-zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more non-zeolitic molecular sieves being effected under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
78. The process of claim 77 wherein the one or more amine starting materials are selected from substituted and unsubstituted cyclic amines, acyclic amines, alkylenediamines, alkanolamines, alkylamines and polyalkylene polyamines.
79. The process of claim 77 wherein the one or more amine starting materials are selected from piperazine, ethylenediamine, monoethanolamine, isopropanolamine, diisopropanolamine, aminoethylethanolamine, N-(2-hydroxyethyl)-piperazine, N-(2-aminoethyl) piperazine, diethanolamine, triethanolamine, tris(2-aminoethyl)-amine, morpholine, diethylenetriamine and triethylenetetraamine.
80. The process of claim 77 wherein the one or more amine starting materials are selected from piperazine, ethylenediamine, monoethanolamine, N-(2-aminoethyl)ρiperazine and N-(2-hydroxyethyl)-piperazine.
81. The process of claim 77 wherein the one or more amine starting materials include piperazine and an alkylenediamine.
82. The process of claim 77 wherein the one or more amine starting materials include piperazine and ethylenediamine.
83. The process of claim 77 wherein the one or more amine starting materials are selected from piperazine, ethylenediamine and isopropanolamine.
84. The process of claim 77 which further comprises contacting one or more amine starting materials and optionally one or more non-amine starting materials with one or more non-zeolitic molecular sieves.
85. The process of claim 84 wherein the one or more non-amine starting materials include diols.
86. The process of claim 84 wherein the one or more non-amine starting materials include ethylene glycol and propylene glycol.
87. The process of claim 77 wherein at least one of the amine starting materials is converted into triethylenediamine and/or one or more of pyrazine, substituted pyrazines, pyridine, substituted pyridines, piperidine, substituted piperidines, piperazine, substituted piperazines, aminoethylethanolamine, diethanolamine, ethylenediamine, allylamines, substituted triethylenediamines, morpholine and substituted morpholines.
88. The process of claim 77 wherein at least one of the amine starting materials is converted into triethylenediamine and/or one or more of pyrazine or substituted pyrazines.
89. The process of claim 77 wherein at least one of the amine start ing materi als is converted into triethylenediamine and/or one or more substituted triethylenediamines.
90. The process of claim 77 wherein at least one of the amine starting materials is converted into triethylenediamine or 1,4-diazabicyclo[2.2.2]octane (DABCO) and/or 2-methyl-triethylenediamine or 2-methyl-1,4-diazabicyclo[2.2.2]octane (methyl DABCO).
91. The process of claim 77 wherein the non-zeolitic molecular sieve comprises a modified non-zeolitic molecular sieve or mixtures thereof.
92. The process of claim 77 wherein the non-zeolitic molecular sieve has an empirical chemical composition on an anhydrous basis expressed by the formula I:
(I) mR(QwAlxPySiz)O2
where "Q" represents:
(a) at least one element present as a framework oxide unit "QO 2 n " with charge "n" where "n" may be -3, -2, -1, 0 or +1; or
(b) an element having:
(i) a mean "T-O" distance in tetrahedral oxide structures between about 1.51 Angstroms and about 2.06 Angstroms,
(ii) a cation electronegativity between about 125 kcal/gm-atom to about 310 kcal/gm-atom, and (iii) the capability of forming stable Q-O-P, Q-O-Al or Q-O-Q bonds in crystalline three dimensional oxide structures having a "Q-O" bond dissociation energy greater than about 59 kcal/gm-atom at 298°K; "R" represents at least one organic templating agent present in the intracrystalline pore system;
"m" represents the molar amount of "R" present per mole of (CwAlxPySiz)O2 and has a value from zero to about 0.3; and
"y" and "z" represent the mole fractions of QO2 n, AlO2-, PO2 +, SiO2, respectfully, present as framework oxide units; and the mole fractions of "Q" , aluminum, phosphorus and silicon, respectively, present as framework oxides said mole fractions being within the following limiting compositional values: w is equal to 1 to 98 mole percent; y is equal to 1 to 99 mole percent; x is equal to 1 to 99 mole percent; and z is equal to 0 to 98 mole percent.
93. The process of claim 77 wherein the non-zeolitic molecular sieve is selected from AlPO4, SAPO, MeAPO, MeAPSO, ELAPO and ELAPSO molecular sieves and mixtures thereof.
94. The process of claim 77 which is carried out at a temperature of about 250°C to about 500°C.
95. The process of claim 94 which is carried out at a temperature of about 350°C to about 425°C.
96. The process of claim 77 which is carried out at a pressure of from about atmospheric to about 5000 psig.
97. The process of claim 96 which is carried out at a pressure of from about atmospheric to about 1000 psig.
98. The process of claim 77 wherein the one or more amine starting materials are in the gaseous phase while being contacted with the one or more non-zeolitic molecular sieves.
99. The process of claim 98 wherein the one or more amine starting materials are mixed with a carrier gas while being contacted with the one or more non-zeolitic molecular sieves.
100. The process of claim 99 wherein the carrier is nitrogen, ammonia or steam.
101. The process of claim 77 wherein the contacting of the one or more amine starting materials with the one or more non-zeolitic molecular sieves occurs under oxidizing conditions.
102. The process of claim 77 wherein the contacting of the one or more amine starting materials with the one or more non-zeolitic molecular sieves occurs in the presence of water or steam.
103. The process of claim 99 wherein the one or more amine starting materials comprise from about 1 to about 95 mole percent of the total feed of starting material and carrier.
104. The process of claim 103 wherein the one or more amine starting materials comprise from about 9 to about 30 mole percent of the total feed of starting material and carrier.
105. A process for the conversion of piperazine to at least one of triethylenediamine, pyrazine, substituted pyrazines, aminoethylethanolamine, diethanolamine, substituted triethylenediamines, morpholine and substituted morpholines, which process comprises contacting the piperazine with one or more non-zeolitic molecular sieves, the contacting of the piperazine with the one or more non-zeolitic molecular sieves being effected under conditions effective to convert the piperazine into at least one of said products.
106. A process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more molecular sieves being effected in the presence of water or steam and under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
107. The process of claim 106 wherein the one or more amine starting materials are selected from substituted and unsubstituted cyclic amines, acyclic amines, alkylenediamines, alkanolamines, alkylamines and polyalkylene polyamines.
108. The process of claim 106 wherein the one or more amine starting materials are selected from piperazine, ethylenediamine, monoethanolamine, isopropanolamine, diisopropanolamine, aminoethylethanolamine, N-(2-hydroxyethyl)-piperazine, N-(2-aminoethyl) piperazine, diethanolamine, triethanolamine, tris (2-aminoethyl) amine, morpholine, diethylenetriamine. and triethylenetetraamine.
109. The process of claim 106 wherein the one or more amine starting materials are selected from piperazine, ethylenediamine, monoethanolamine, N-(2-aminoethyl)piperazine and N-(2-hydroxyethyl)-piperazine.
110. The process of claim 106 wherein the one or more amine starting materials- include piperazine and an alkylenediamine.
111. The process of claim 106 wherein the one or more amine starting materials include piperazine and ethylenediamine.
112. The process of claim 106 wherein the one or more amine starting materials are selected from piperazine, ethylenediamine and isopropanolamine.
113. The process of claim 1 which further comprises contacting one or- more amine starting materials and optionally one or more non-amine starting materials with one or more molecular sieves.
114. The process of claim 113 wherein the one or more non-amine starting materials include diols.
115. The process of claim 113 wherein the one or more non-amine starting materials include ethyene glycol and propylene glycol.
116. The process of claim 106 wherein at least one of the amine starting materials is converted into triethylenediamine and/or one or more of pyrazine, substituted pyrazines, pyridine, substituted pyridines, piperidine, substituted pipefidines, piperazine, substituted piperazines, aminoethylethanolamine, diethanolamine, ethylenediamine, allylamines, substituted triethylenediamines, morpholine and substituted morpholines.
117. The process of claim 106 wherein at least one of the amine starting materials is converted into triethylenediamine and/or one or more of pyrazine or substituted pyrazines.
118. The process of claim 106 wherein at least one of the amine starting materials is converted into triethylenediamine and/or one or more substituted triethylenediamines.
119. The process of claim 106 wherein at least one of the amine starting materials is converted into triethylenediamine or 1,4-diazabicyclo[2.2.2] octane (DABCO) and/or 2-methyl-triethylenediamine or 2-methyl- 1,4-diazabicyclo[2.2.2]octane (methyl DABCO).
120. The process of claim 106 wherein the molecular sieve comprises a silica molecular sieve or mixtures thereof.
121. The process of claim 106 wherein the molecular sieve comprises a modified silica molecular sieve or mixtures thereof.
122. The process of claim 120 wherein the silica molecular sieve is selected from Silicalite, Silicalite II, fluoride Silicalite and mixtures thereof.
123. The process of claim 120 wherein the silica molecular sieve is Silicalite or modified Silicalite.
124. The process of claim 106 wherein the molecular sieve comprises a non-zeolitic molecular sieve or mixtures thereof.
125. The process of claim 106 wherein the molecular sieve comprises a modified non-zeolitic molecular sieve or mixtures thereof.
126. The process of claim 124 wherein the non-zeolitic molecular sieve has an empirical chemical composition on an anhydrous basis expressed by the formula I:
(I) mR(QwAlxPySiz)O2
where "Q" represents:
(a) at least one element present as a framework oxide unit "QO2 n" with charge "n" where "n" may be -3 , -2, -1, 0 or +1; or
(b) an element having:
(i) a mean "T-O" distance in tetrahedral oxide structures between about 1.51 Angstroms and about 2.06 Angstroms,
(ii) a cation electronegativity between about 125 kcal/gm-atom to about 310 kcal/gm-atom, and
(iii) the capability of forming stable Q-O-P, Q-O-Al or Q-O-Q bonds in crystalline three dimensional oxide structures having a "Q-O" bond dissociation energy greater than about 59 kcal/gm-atom at 298°K; "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (QwAlxPySiz)O2 and has a value from zero to about 0.3; and "w", "x", "y" and "z " represent the mole . fractions of QO2 n, AlO2-, PO2 +, SiO2, respectfully, present as framework oxide units; and the mole fractions of "Q", aluminum, phosphorus and silicon, respectively, present as framework oxides said-mole fractions being within the following limiting compositional values: w is equal to 1 to 98 mole percent; y is equal to 1 to 99 mole percent; x is equal to 1 to 99 mole percent; and z is equal to 0 to 98 mole percent.
127. The process of claim 124 wherein the non-zeolitic molecular sieve is selected from AlPO4, SAPO, MeAPO, MeAPSO, ELAPO and ELAPSO molecular sieves and mixtures thereof.
128. The process of claim 106 wherein the molecular sieve comprises a zeolitic molecular sieve or mixtures thereof.
129. The process of claim 106 wherein the molecular sieve comprises a modified zeolitic molecular sieve or mixtures thereof.
130. The process of claim 128 wherein the zeolitic molecular sieve is selected from A-type zeolitic molecular sieves, X-type zeolitic molecular sieves, Y-type zeolitic molecular sieves, L-type zeolitic molecular sieves, mordenite, LZ-10, LZ-210, LZ-211, LZ-212, LZ-227, omega zeolitic molecular sieves, LZ-202, LZ-105 and mixtures thereof.
131. The process of claim 128 wherein the zeolitic molecular sieve is selected from ZSM-5,
ZSM-11, ZSM-12, ZSM-20, ZSM-34, omega zeolite, beta zeolite and mixtures thereof.
132. The process of claim 106 which is carried out at a temperature of about 250°C to about 500°C.
133. The process of claim 132 which is carried out at a temperature of about 350°C to about 425°C.
134. The process of claim 106 which is carried out at a pressure of from about atmospheric to about 5000 psig.
135. The process of claim 134 which is carried out at a pressure of from about atmospheric to about 1000 psig.
136. The process of claim 106 wherein the one or more amine starting materials are in the gaseous phase while being contacted with the one or more molecular sieves.
137. The process of claim 136 wherein the one or more amine starting materials are mixed with a carrier while being contacted with the one or more molecular sieves.
138. The process of claim 137 wherein the carrier is nitrogen, ammonia or steam.
139. The process of claim 106 wherein the contacting of the one or more amine starting materials with the one or more molecular sieves occurs under oxidizing conditions.
140. The process of claim 137 wherein the one or more amine starting materials comprise from about 1 to about 95 mole percent of the total feed of starting material and carrier.
141. The process of claim 140 wherein the one or more amine starting materials comprise from about 9 to about 30 mole percent of the total feed of starting material and carrier.
142. A process for the conversion of piperazine to at least one of triethylenediamine, pyrazine, substituted pyrazines, aminoethylethanolamine, diethanolamine, substituted triethylenediamines, morpholine and substituted morpholines, which process comprises contacting the piperazine with one or more molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves, the contacting of the piperazine with the one or more molecular sieves being effected in the presence of water or steam and under conditions effective to convert the piperazine into at least one of said products.
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