CA1310668C - Chemical conversion process - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A process for converting a feedstock containing 1 to about 6 carbon atoms per molecule which includes (a) contacting the feedstock with a solid composition comprising a crystalline microporous three dimensional solid catalyst having pores and being capable of promoting the conversion, and matrix material at conditions effective to convert the feedstock, to produce at least one desired product, and to at least partially deactivate the solid composition; (b) contacting the deactivated solid composition with regeneration medium at conditions to at least partially regenerate the solid composition; and (c) repeating step (a), the improvement which comprises (d) contacting the regenerated solid composition prior to step (c) to condition the regenerated solid composition to have increased effectiveness in step (c).

Description

n-15671 1 31 06~

C~IEMICAL CONVERSION PROCESS

Field of the Invention This invention relates to a chemical conversion process employing a catalyst. More particularly, the invention relates to such a chemical converslon process employlng certain defined catalysts which provides outstandlng results.
Background of the Invention Chemical conversion employlng solid catalysts are often conducted using a fixed, ebullating, moving or fluidized bed of catalyst-containing particles. Also, catalyst/liquid slurry reaction systems may ~e utilized.

Crystalline microporus three dimensional solid catalysts or CMSCs, i.e., catalysts which promote chemical reactions of molecules having selected sizes, shapes or transition states, lnclude naturally occurring molecular sieves and synthetlc molecular sleves, together referred to as molecular sieves, and layered clays.
~ j ~ ~ I ()6~

CMSC-containing particles often include one or more matrix materials, such as binders and fillers, to provide a desired property or properties to the particles. These matrix materials often promote undesirable chemical reactions or otherwise detrimentally affect the catalytic performance of the CMSC. It would be advantageous to reduce the deleterious effect of such matrix materials on the catalytic performance or effectiveness of solid compositions containing CMSC and one or more of such matrix materials.
Methanol is readily producible from coal and other raw materials by the use of well-known commercial processes~ For example, synthesis gas can be obtained by the combustion of any carbonaceous material including coal or any organic material such as hydrocarbons, carbohydrates and the like. The synthesis gas can be manufactured into methanol by a well known heterogeneous catalytic reaction.
"Hydrocarbons from Methanol" by Clarence D. Chang, published by Marcel Dekker, Inc. N.Y. (1983~ presents a survey and summary of the technology described by its title. Chang discussed methanol to olefin conversion in the presence of molecular sieves at pages 21-26. The examples given by Chang as suitable molecular sieves for converting methanol to olefins are Chabazite, erionite, and synthetic zeolite ZK-5.

, 13tO6~
~ .S. Patents 4,238,631; and 4,423,274 disclose processes for converting methanol to olefin-enriched or gasoline boiling range hydrocarbons in the presence of fluid catalyst particles having a zeolite with a pore opening of at least 5 angstroms.
These zeolites are distinguished by virtue of having an effective pore size intermediate between the small pore Linde A and the large pore Linde X, i.e., the pore windows of the structure are the size which would be provided by 10 member rings of silicon atoms interconnected by oxygen atoms. These zeolites include ZSM-5, ZSM-ll, ZSM-12, ZSM-23, ZSM-35, ZSM-38, and ZSM-48. These patents disclose that such intermediate pore size zeolites can be utilized by maintaining a high coke level on the catalyst, in the range of 5 to 20 weight ~, to preferentially produce olefins. U.S. Patent 4,079,095 discloses a process for making light olefins from methanol using ZSM-34, which is a zeolite having a pore size somewhat smaller than the zeolites described in the other patents noted in this paragraph. However, no olefin selectivity advantage for maintaining a high coke level was disclosed when using the smaller pore ZSM-34 zeolite.
U.S. Patents 4,300,011 and 4,359 ,595 disclose processes for alkylating aromatics and converting methanol to gasoline and/or olefins (among other reactions) catalyzed by the above-noted intermediate sized zeolites with bulky heterocyclic organic nitrogen compounds, e.g., quinoline. These patents disclose that the production of unwanted products is suppressed. Th~se patents disclose that the nitrogen compounds may be effective as heat J 6 6 ~

transfer mediums or solvents for the reaction. Neither patent discloses smaller pore zeolites, catalyst regeneration nor slurry reactions.
Amonq the CMSC8 that can be used to promote converting methanol to olefins are non-zeolitic molecular sieves such as aluminophosphates or ALPOs, in particular silicoaluminophosphates or SAP0~ disclosed in U.S. Patent No. 4,440,871. U.S. Patent 4,499,327, issued February 12, 1985 dioclo6es processes for catalytically converting methanol to light olefins using SAPOs at effective process conditions.
Summary of the Invention A process for catalytically converting a feedstock has been discovered. In one broad aspect, the present process involves converting a feedstock containing 1 to about 6 carbon atoms per molecule with a solid composition, e.g., solid particles, comprising crystalline microporous three dimensional solid catalyst or CMSC having the ability to promote the conversion and matrix material component at conditions effective to convert the feedstock and to produce at least one desired product. The present improvement comprises conditioning at least a portion of this solid composition prior to and/or during the feedstock/solid composition contarting to provide a solid composition having increased effectiveness in the feedstock/solid composition contacting.

A

13~()GG~3 Discussion of the Invention The present catalytic conversion process provides substantial advantages. For example, the often relatively non-selective catalytic activity of the matrix material, e.g., binder and filler, component of the solid composition can be substantially reduced or even substantially eliminated by employing the present conditioning step. This benefit is achieved without substantially adversely impacting on the structure or desired functioning of the matrix material. This conditioning step, which is preferably separate and apart from the conventional catalyst regeneration step, can result in more effective feedstock utilization and increased desired product yields. In many instances, the conditioning step involves the use of relatively inexpensive materials and/or relatively small amounts of such materials. In short, the present invention can provide a cost effective processing route to improved yields of desired products.

In one embodiment, the feedstock/solid composition contacting further involves at least partially deactivating the solid composition, e.g., by the disposition of carbonaceous deposit material on the solid composition. This deactivation causes the solid composition to be less active in promoting feedstock conversion, e.g., to the desired product. The 131U~

~eactiv~ted solid cor:~r~osition is contacte3 ~..ith re,eneration r.~e~iun~, e.g., an oV.~gen-containin~ ~aseous ~::ediu;:~, at conditicl:~
effective to at least partiall~ reeenerate ~ie soli~l co~: ocitior., i.e., to at 1east ~artiall~,- restore '_}:e activiti to t'^.e scli' co::~r~o~iticsl tc rror~ote fee_stock col:vGi-ioll, e.,., to tl.~G _esi~e-_ r!roduct. '~'ne fGed_tock/soli~ cor.trocitics~ co~:tacti.~ t':er:
rereated. I-: this ~ odi;::~r-t, t!~e pr se~lt i.:pro~e.:GI:t co~ isea contactin~ the re~,er.er2te~_ cat~lyct ~L ior tc re;,eatil~ ''G
feedstock~solid co:::L,ositi_n contactir:y to con'ition t'e re~,enerated soli~ co~ osition to h ve increaaed el-fectlveneâj i!l t~e rereated .eecstook/solid co;::rosition cor':Gctil-;- rel~ti~JG to t}le Le~enerate- soli_ cc:::rosition ~.?itho~t tle rrGaGnt co~l~itio~.iz~
In anot~er er~odi.:~ent, ri~e ;rc~erlt i~ Lo~e-~:ent col:rprises contactin~ at least one co.;!L.:or.cnt, e.~., at l-~.at o e :::atri~ ateri-l co~::ponent, o the soli~ co~i:L,ositicn rrior to t'e fee~1stoc!/solid cc~:~rosition contactin.g to L-o~ e t'.e ~oll: -coi~positicn ~ith increaseæ effectiveness in t~:e fee st^c,v/~
Co~.F~osition CCnt2Ctins.
In a urt'ner e~hodir.ent, tlle soli_ co::ro_iti_l~ -i the feedstock/solid co::lpositior. contactin~ is preaellt ~s soli!
particles in tlle fluidized state or in a fiv~ed be~d, rreferabl,~
in the flui~ized state. In t~is er:.'~odi~.ent, t!:e present ~1066~

in~rrove~ent co~ ri~es con~uctir:~, tie fee~stock/soli ~articles contactir~ ti'l rLes'rlce Of at least cne ac`ced con~itior-ir:~
a~ent ir. an .~:cunt eLEcc';ive to i~ rove tie erfor::al:ce cf tle soll~ ~articler- in tl-:e Eeedstoc~./sclid r~artirles ccntactinS, rrcvi ed t:~t ~i:e cor:ditic:lir~ a~nt is su~stc~rlti- 1,~ _r_~le cf er.Leril:c, tl.e rore~ of t!.e C.7~C. rr:us/ t!e conditicr:in~ =~er.t Cal` :~er:~fici~ aLLect ti:e ~_tri~ _teri_1 cc:-por:ent o- t~e soli~ ,~articles, ~ ch `lavl.n~ su~stantially no averse ef ect cr:
tlle C~i~C cc::L~oner.t cf t:e ~oli~t r~articlec.
~ ctl cf t~e above ti:ree ~ c~ ents r;:a~ J_ L L-._tiC'~
ir:deJe:!~er:tl,~, i.e., ~lt:cut Leferer:ce to ti:e c ier t~;7c CI~;JO i:::ents. ;.o~.~ever, c~ni~ t~:!o or 211 tl:ree ^~ t.:ese e-:_odi ent_ ::ay ;c rracticed at one til;:e, T.~.~ in tlie s~r.~e cor:T:erci~l c er2ticn. In ^tl~er -~..or~J_, t}~ese e:bodi ents are nct r,eceCc~ri e~.clusive of each cthner ~ncl 7T~ay ~e 2c`~Jar:ta~eousl~ r~rt-ced in V2 ricus ccci~inations.
~ s r:ote~ _bove, C.~Cs are tl:ose ~--:L Ci! LOfO ::ote '. e :'i' re~ctiors of :::oiecules i~avin~ selTctT--~ _izes, si:2r~e~ cr tr~rlsiticn st~teC. That is, C~Cs 2re ~!~terials ~ icl~ L?r_.;:otG
~e.:!ical reactions of Eeedstoc~ l::olec~les l;?i:ich co~Eor-:: tc ~ e~ lcc~12r cize, ~olecul2r share or n.:oleculaL transitio:~
state constrcLint. 7~iEferent C7.~C r.ave cifEere~-Lt size/sl~aLre/tran3ition state constraints deper~ir~ on t:.e Lh~sical 1 3.1:~G~

structure and chemical composition, for example, the average effective diameter of the pores, of the CMSC. Thus, the particular CMSC chosen for use depends, for example, on the particular feedstock employed, and on the particular chemical conversion (reaction) and product desired. Preferably, the CMSC
has a substantially uniform pore structure, e.g., substantially uniformly sized and shaped pores. CMSC's include, for example, layered clays; zeolitic molecular sieves and non-zeolitic molecular sieves or MZMS's.
The presently useful MZMS's include molecular sieves embraced by an empirical chemical composition, on an anhydrous basis, expressed by the formula:
(I) mR: (QwAlxpysiz)o2 where "Q" represents at least one element present as a framework oxide unit "C02n" with charge "n" where "n" may be -3, -2, // ~\
/
!~ \

~ ~ 8 1 3 1 ~)6~
-1, or ll; "R" represents at least one or~anic templatlng agent present on the ~ntracrystalline pore system; "m"
,- represents the molar amount of "R" present per mole of tQWAlXP~ iz)02 and has a value from zexo to about 0.3;
and "w", "x", "y" and "z" represent the mole fractions of QO2n, AlO2-; PO2+, SiO2, respect~vqly, present as framework oxide units. "Q" is characterized as an element hav$ng a mean "T-O" distance in tetrahedral oxide structures ~etween about 1.51 A and about 2.06 A. "Q" has a cation electronegativlty between a~cut 125 kcalfg-atom to about 310 kcal/~m-atom and "Q" is capàble of forming stable Q-O-~, Q-O-Al or Q-O-Q bonds in crystalllne three d~mensional oxide structures having a "Q-O" bond dissaciation energy greater than about 59 kcal/g-atom at 298~1; and "w", "x", "y" and "z" represe~t the mole fract~ons of "Q", aluminum, phosphorus and silicon, respectlvely, present as ~ramework oxides said mole fractions bei~g within the lLmitin~ compositional values or points as follows:
w is equal to 0 to 99 mole percent;
y is e~ual to 1 to 99 mole percent;
x is egual to 1 to 99 mole percent; and z is equal to 0 to 99 mole percent.
The "Q" of the "QAPSO" molecular sieves pf formula ~I) may be def~ned as representing at least one element capable of forming a ~ramewor~ tetrahedral ox~de and may be one of ~he l See the discussion at pages 8a, ab and 8c of E~C Publi~ation 0 159 624, publ$shed October 30, 1985, about the characterization of #EL~ and "~. Such are equivalent to Q as used herein.

I 3 1 ~6~

elements arsenic, berrylium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese~ titanium, vanadium and zinc. Combinations of the elements are contemplated 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 aluminophosphate or AlP04. Where z has a positive value, then the operative structure is that of silicoaluminophosphate or SAPO. 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's and ELAPO's or MeAPO's or MeAPSO's, 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 compositions and structures described in the patents and patent applications set forth in Table A, which follows, and by Flanlgen et al., in the paper entitled, "Aluminophosphate '' y 10 1 3 1 0 G 6f~

Molecular Sieves and the Periodic Table," published in the "New Developments and Zeolite Science Technology, Proceedings of the 7th International Zeolite Conference, edited by Y. Murakami, A.
Sijima and J. W. Ward, pages 103-112 (1986):

! `, ~

"`...
", TABLE A ~ G ~
Patent or Pat.
Applic. No. Subiect Matter of Patent or Patent AP~1~ cation U.S. MAPO's are crystalline metal Pat. 4, 567, 029 aluminophosphates having a three-dimensional microporous framework structure of ~02-2, AlO2- and PO2+ tetrahedral units and havïng an empirical chemical composition on an anhydrous basis expressed by the formula mR:(MxAlyPz)02; where R represents at least one organic templating agent present in the intracrystalline pore system; _ has a typical value of from 0 to 0.3 and represents the moles of R present per mole of ~MxAl~Pz)O2; M represents magnesium, manganese, zinc or cobalt, x, y and z represent the mole fractions of M, aluminum and phosphorus, respectively, present as tetrahedral oxides. The fractions are such that they are within a tetragonal compositional area defined by points A~C and D of Figure 1 of the drawings of the patent.
This patent, at column 6, describes the use of aluminophosphates as a source of phosphorus (lines 26~28) and as a source o~ aluminum (lines 38-40), and the use of seed crystals to aid in the crystallization of ~he desired molecular sieve (lines 59-63). Example 85 depicts ~he use of MAPO-36 as a seed for making Mn.APO-36. The chemical composition of the MnAPO-36 fails to reveal the presence of any magnesium.

~ 3 1 0&~
U~ SAPO molecular sieves are a general class Pat.4,440,871 o~ microporous crystallilne silicoaluminophosphates. The pores have a nominal diameter of greater than about 3 A. The "essentially empirical composition" is mR:(SixAlyPz)02~ where R represents at least one organic templating agent present in the intracrystalline pore system; m has a typical value of from O to 0.3 and represents the moles of R present per mole of (SiXAlyPz)02; x, y and z represent the mole fractions of silicon, aluminum and phosphorus, respectively, present as tetrahedral oxides. The fractions are such that they are within a pentagonal compositional area defined b~ points A, B, C, D and E of the ternary diagram of Figure 1 and preferably within the pentagonal compositional area defined by points a, b, c, d and e of Figure 2, of the drawin~s of the patent. The SAPO
molecular sieves have a characteristic x-ray powder diffraction pattern which contains at least ~he d-spacings set forth in any one of Tables I, III, V, VI~, IX, XI, XIII, XV, XVII, XIX, XXI, XXIII or XXV of the patent. Further, the as-synthesized crystalline sili~oaluminophosphates of the patent may be calcined at a temperature sufficiently high to remove at least some of any organic templating agent present in the intracrystalline pore system as a result of such synthesis. The silicoaluminophosphates are generally referred to therein as "SAPO", as a class, or as 1 3 1 06~
"SAPO-n" wherein "n" is an integer denoting a particular SAPO as its preparation is reported in the patent.
The U.5. patent speaks at column 8, lines 12-16 of employing seed crystals to generate SAPO species. That technique is described in examples 22, 51 and 53.

ELAPSO molecular sieves have the units U.S. Patent No. ELO2~, AlO2-, PO2+, SiO2 in the 4,793,984 framework structure and have an empirical commonly chemical composition on an anhydrous basis assigned, EPC expressed by ~he formula:
Public. O 159 mR:~ELwAlxpysiz)o2 624, published where "EL`' represents at least one element October 30, present as a framework oxide unit "ELO2n"
1985 with charge "n" where "n" may be -3, -2, -1, 0 or +1; "R" represents at least one organic ~emplating agent present on the intracrystalline pore system; "m" represents ~he molar amount of "R" present per mole of (EL~AlxPySiz)O2 and has a value from zero to about 0.3; and "w", "x", "y" and "z"
repesent the mole fractions o~ ELO2n, AlO2-, PO2+, SiO2, respectively, present as framework oxide units. "EL" is characterized as an element having (a) a mean "T-O" distance in tet~ahedral oxide structures between about 1.51 A and about 2.06 A, (b) a cation electronegativity between about 125 kcal/g-atom to about 310 kcal/gm-atom and (c) a capability of forming stable M-O-P, M-O-Al or M-O-M bonds in crystalline th~ee dimensional 13~066~3 oxide structures having a "m-O" bond dissociation energy greater than about 59 ~cal/g-atom at 298R. "w", "x", "y" and "z~' represent the mole fractions of "EL", aluminum, phosphorus and silicon, respectively! present as framework oxide~. The mole fractions are within ~he limitin~ compositional values or points as follows:

Mole Fraction Point x Y ~z + w) ~ , ~ ~
A 0.60 0.39-(O.Olp) O.Ol(p + 1) B 0.39-(O.Olp) 0.60 O.OltP + 1) C 0.01 0.6~ 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 which "EL" represents in the ~E~wAl~PySiz)O~ composition.
The "EL" of the "ELAPSO" molecular sieves may be defined as representin~ at least one element capable of forming a framework tetrahedral oxide and is preferably 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, respective~y, present at tetrahedral oxides in which the mole 6 ~ ~
fractions are within the limiting compositional values or points as follows:
_ Mole Fraction _ _ Point x v _ (z + w) __ a 0.60 0.3~-(O.Olp) O;Ol(p + 1) b 0.39-(O.Olp) 0'60 O.Ol(p + 1 c 0.10 0.55 0.35 d Q.55 0.10 0.35 where "p" is as above defined.
The EP publication at page 16 discloses the use of crystalline and amorphous aluminophosphate as a source of phosphorus and aluminum and at page 17 describes seeding the reaction mixture. Examples llA, 12A, 93A-103A, 5B, 6~, 55~, 58~, 598, 50D-56D, S9D-62D and 12F-15F depict the use of seed crystals.

U.S. Pat. TAPO molecular sieves comprise 4,500,651, three-dimensional microporous crystalline patented Feb. framework structures of [TiO2], [A102] and 19, 1985 [P02] tetrahedral units which have a unit empirical foxmula on an anhydrous basis of:

mR:(TixAlypz)o2 (1) wherein "R" represents at least one organic templating agent present in the intracrystalline ~ore system; "m" represents the moles of "R"
present per mole of (TiXAlyPz)02 and has a value o~ from zero t~ 5.0, the maximum value in each case depending upon the molecular dimensions of the templating agent and the i6 l~tU6'`~
available void volume of the pore system of the particular titanium molecular sieve; "x", "y"
and "z" represent the mole fractions of titanium, aluminum and phosphorus, respectively, present as tetrahedral oxides, representing the following values for "x", "y" and "z":

Mole Fraction Point x Y ~z + w) A 0.001 0.45 0.549 B 0.88 0.01 0.11 C 0.98 0.01 ~.01 D 0.29 0.70 0.01 E OoOOOl 0~70 0~299 The parameters "x", "y" and "z" are preferably within the following values for "x", "y" and "z":
~ole Fraction Point x v (z ~ w~
__ __ .
a 0.002 0.499 0.499 b 0.20 0.40 ~.40 c ~.20 0.50 0.30 d 0.10 0.60 0.30 e 0.002 0.~0 0.398 The TAPO molecular sieves are generally furtller characteri2ed by an intracrystalline adsorption capacity for water at 4.6 torr and about 24~C., of about 3.0 weight percent. The adsorpeion of water has been observed to be completely reversible while re~aining the same 1310~'6~
essential framework topology in both the hydrated and dehydrated state.

The U. S. patent at column 8, lines 65-6~, and column 9, lines 15-18, discusses the use cf crystalline amorphous aluminophosphate as a souxce of phosphorus and aluminum. At column 6, lines 1-5, æeedinq is described as facilitating the crystallization procedure. Comparative example 44 describes a composition of amorphous TiO2 and 95 wt. % AlP0418 without an indication of how the composition was prepared.

U.S. Patent No. The TiAPSO molecular sieves have 4,684,617 three-dimensional microporous framework EPC Public. structures of TiO~, A102, O 161 488, PO~ and SiO2 tetrahedral oxide units published havin~ an empi~ical chemical composition on an Nov. 21, 1985 anhydrous basis expressed by the formula:

~ TiWAlXpysiz ) o2 whe~ein "X" represents at least one organic templating agent present in the intracrystalline pore system; "m" represen~s the molar amount of "R" present per mole of (TiwAlxPySiz)02 and has a value of from zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of titanium, aluminum, phosphorus and silicon, respectively, D

t3tO6~
present as tetrahedral oxides and each has a value of at least 0.01. The mole fractions "w", "x", "y" and "z" are ~enerally defined in respect to the ternary diagram of F$gure 1 of the applications as being within the following limiting compositional values or points:

Mole Fraction Point ~ x Y (z + w) A 0.60 0.38 0.02 3 0.38 0.~0 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 subclass of TiAPSO molecular sieves the values "w", "x", "y" and "z" in the above formula are within the tetragonal compositional area defined by points a, b, c and d of the ternary diagram of Figure 2 of the aplications, said points a, b, c and d representing the following values for "w", "x", "y" and "z":

Mole Fraction Point x (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 The publication, a~ page 13, describes the use of crystalline or amorphous aluminophosphate as a source of phosphorus and aluminum and, at page 14, paints out that 1~

1 3 1 () 6 ~ ~

seeding the reaction mixture facilitates the crystalline procedure.
U.S. Pat. Ferroaluminophosphates (FAPO's) are 4,554,143, disclosed in U.S. Patent No. 4,554,143, patented Nov. and have a three-dimensional microporous 19, 1985 crystal framework ~tructure of A102, FeO2 and PO2 tetrahedral units and have an essential empirical composition, on an anhydrous basis, of:
mR: (FexAlypz)o2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m"
represents the moles of "R" present per mole of (PexAlyPz)O2 and has a value of from zero to 0.3, the maximum value in each case depending upon the molecular dimen6ions of the templating agent and the available void volume of the pore system of the particular ferroaluminophosphate involved; "x", "y"
and "z" represent the mole fractions of iron, aluminum and phosphorus, re~pectively, pre~ent a~ tetrahedral oxides, representing the following values for ~xn, ny~ and nzn ., ~ 3 1 U66~
Mole Fraction Point _ x ~~ l ~z + w) . 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 When synthesized the minimum value of "m" in the formula above ~s 0.02. In a preferred subclass of the ferroaluminophosphates the values of "x", "y" and "z" in the formula above are representing the following values of "x", "y" and "z":
__ Mole Fraction Point x Y ~z + w) a 0.01 0.52 0.47 b 0.01 0.39 0.60 c 0.25 0.15 0.60 d 0.25 0.40 0.35 The iron of the FeO2 structural units can be in either the ferric or ferrous valence state, depending largely upon the source of the iron in the synthesis gel. Thus, a FeO2 tetrahedron in the structure can have a net charge of either -1 or -2.
The patent indicates at column 5, lines ~3-45 and 54-56, that crystalline amorphous aluminophosphate may be used as a source of phosphorus and aluminum and at column 6, lines 1-5, describes seeding o~ the reaction mixture as facilitating the crystallization procedure.

U.S. Patent No. The FeAPSO molecular sieves have a ,683,317, EPC three-dimensional microporous crystal framework Publication structures of FeO2~2 (and~or FeO2), o 161 491, AlO2, PO2 and SiO2 tetrahedral oxide published units and having a unit empirical formula, on Nov. 21, 1985 an anhydrous basis, of:
mR:5FewAlxpysiz)o2 (1) wherein "R" represents at least one organic templatin~ agent present in the intracrys~alline pore system; "m" represents the moles of "R" present per mole of (FewAlxPySiz)O2 and has a value o~
from zero to about 0.3; the maximum value of "m" in each case depends upon ~he molecular dimensions of the templating agent and the available void volume of the pore system of the particular molecular sieve involved; and "w", "x", "y" and "z" represent the mole fractions of iron, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions bein~ such that they are within the limiting compositional values or points as follows:
_ Mole Fraction Poin~ _x (z + w) A 0.60 0.38 0.02 0.38 0.60 0.02 C 0.01 0.60 0.39 D Ø01 0.01 0.98 E 0.60 0.01 Ø39 The values of w, x, y and z may be as follows:

gl~ ` .

1 3 1 066~
_ Mole Fraction Point x __X__ (z ~ wj a 0.55 0.43 0.02 b 0.43 O.S5 0.02 c 0.10 0.55 0.35 d 0.55 0~10 0.35 The ~ publication, at page 12, describes the use of seeding the reaction mixture to facilitate the crystalllzation procedure. At page 18, ~he publication describes the use of crystalli~e amorphous aluminophosphates as a source of phosphorus and aluminum in making the molecular sieve.

U.s. Patent The ZnAPSO molecular sieve~ comprise No. 4,935,216, framework structures of ZnO2 2, A102-, EPC PO2+ and sio2 tetrahedral units haviny an Publication empirical chemical composition on an anhydrous 0 158,975, basis expressed by the formula:
published Oct.
23, 1985 mR:(znwAlxpysiz)o2 wherein "R" represents at least one organic templating agent present in ~he intracrystalline pore system; "m" represents the molar amount of "R" present per mole of 1Z~wAlxPySiz)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, presen~ as D

066~
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 _ 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 O.SS 0.10 0O35 This publication at page 13 discloses that crystalline or amorphous aluminophosphate may b~ used as a source of phosphorus or aluminum and at page 14 indicates that seeding of the r~action mixture with said crystals facilitates the crystallization procedure. Examples 12-15 are stated to employ the seeding procedure.

1 31 06~
Tl,S. Patent The MgAPSO molecular sieves have .~. 4,758,419, three-dimensional microporous framework EPC st~uctures of Mgo2 2, AlO2 , ~2+
Publication and SiO2 tetrahedral oxide units and have an O 158,348, empirical chemical composition on an anhydrous published oct. basis expressed by the formula:
16, 1985 Ir~: (MgwAlxpysiz)o2 wherei~ "R" represents at least one organic templating agent presen~ in the $ntracrystalline pore system; "m" represents the molar amount of "R" present per mole of (MgwAlxPySiz)O2 and has a value from zero to about 0.3; and "w" , "x", "y" and "z"
represent the mole fractions of magnesium, aluminum, phosphorus and silicon, respectively, present as tetxahedral 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 oint ~ x-~- v (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 ;'~
.:. ..

1 3 t Q6~
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 . v ~z ~ w) a 0.55 0.43 0.02 b 0.43 0.55 0.02 c ~.10 0.55 0.35 d 0.55 0.10 0.35 This publication depic~s seeding to generate product at paqe 14 a~d in examples 5, 6, 55, 58 and S9.
U.s. Patent The MnAPSO molecular sieves have a frame-No. 4,686,092, work structure of MnO2, A102, P02, and sio2 EPC Publication tetrahedral units having an e~pirical chemical o 161 490, composition on an anhydrous basis expressed published Nov. by the formula:
11, 1985 m~:(MnwAlxpysiz)o2 wherein "R" represents at least one organic templati~g agent present in the intracrystalline po~e system; "m" representC the molar amount of "R" present per mole of ~MnwAlxPySiz)O2 and has a value of zero to about 0.3t and "w", "x", "y" and "z"
represent the mole fractlons of element manganese, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides.
The mole fractions "w", "x", "y" and "z" are ~ 3 t 0~6~
generally defined as bei~ 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 0.38 E 0.60 0.01 0.39 The values of w., x, y and z may be as follows:

Mole Fraction ~oint 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 The publication at page 13 describes the use oE crystal or amorphous aluminophospha~e as a source of phosphorus or aluminum, and at page 14 characterizes the use of said crystals to facilitate the crystallLzation procedure.
Examples 54~56 and 59-62 state said crystals were used in the manufacture of the MnAPSO
produ~ts.

U.S. Patent The CoAPSO molecular sieves have No. 4,774,970. three-dimensional microporous ~ramework 3~

EPC Publication structures of CoO22, AlO2, PO2 and ~ 3 ~ ~vb~
161 489, SiO2 te~rahedral units and have an empirical published Nov. chemical composition on an anhydrous basis 21, 1985 expressed by the formula:

mR: (CowAlxPysiz)o2 wherein 'IR" represents at least one organic templating agent present in the intrac~ys~alline pore system; "m" represents the molar amount of "R" present per mole of (CowAlxP ~z)2 and has a value of from zero to about 0.3; and "w", "x", ily~l and "z" represents 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 0.38 0.60 0.02 C 0.01 0.60 0.3~
D 0.01 0.01 0.98 E 0.60 0.01 0.39 ln a preferred subclass of the CoAPSO
mol~cular sieves the values of "w", "x", "y"
and "z" in the above ormula are within the limiting compositional values or points as follows:

~8 1~1(J6~(~
r _ 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 The E~ publioation at page 13 depicts the use o~ c nstalline amorphous aluminophosphate as a source of phosphorus and aluminum and at page 14 states that seeding the reaction mixture ~acllitates the crystallization procedure. Examples 11, 12, 13, 93 and 97-103 depict the use of seed crystals.
U.S. Patent MeAPO molecular sieves are crystalline No. 4,686,093, micrsporous alumi~ophosphates in which the EPC substltuent metal is ono of a mixture of two or Publication more divalent me~als of the group magnesium, O 158 976, manganese, zinc and cobal~ and are disclosed in published oct. U.S. ~atent No. 4,567,028. Members of this 23, 1985 novel ~lass of compositions have a three-dimensional microporous crystal framework structure of M022, AlO2 and PO2 tetrahedral units and have the essentially empirical chemlcal com~osition, on an anhydrous basis, of:
mR:(~xAlypz)o2 whorein "R" represents at least one organic templating agen~ present in the intracrys~alline pore system; "m" represents the moles of "R" present per mole of .

(MXAlyPz)O2 and has a value of from 1~ GG~-~zero to 0~3, the maximum value in each case depending upon the molecular dimensions of the templating agent and the available void volume o~ the pore system of the particular metal aluminophosphate involved; "x", "y" and "z"
represent the mole fractions of the metal "M", li.e., magnesium, manganese, zinc and cobalt), aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are representing the following values for "x", "y" and "z":

Mole Fraction Point x~ v t-z~-+ w) A 0.01 0.60 0.39 B 0.01 0.39 0.60 C 0.35 O.OS 0.60 D 0.35 9.60 0.05 When synthesized the minimum value of "m" in the formula above is 0.02. In a preferred subclass of the metal aluminophosphates of this invent~on, the values of "x", "y" and "z" in the formula above are representing the ~ollowing values for "x", "y" and "z":

_ _ Mole Fraction Point x Y (z + w?
~ ~ 0.01 0.52 0.47 b 0.01 0.39 0.60 c 0.25 0~15 0.60 d 0.25 0.40 0.35 3~

1 3 1 06t)~
The as-synthesized compositions are capable of withstanding 350C. calcination in air for extended periods, i.e., at least 2 hours, witho~t becoming amorphous.
The EP publication at pages 14 and 15 depicts the use of crystalline and amorphous aluminophosphate as a source of phosphorus and aluminum and at page 15 states that seeding the reaction mixt~re faoilitates the crystallization procedure. Example 8 discloses seeding of crystals.

EPC "ELAPO" molecular sieves are a class of Publication crys~alline molecular sieves in which at least No. 0158976, one element capable o~ forming published a three-dimensional microporous framework form October 13, crystal framework structures of A102, P02 1985 and EPC and M02 tEtrahedral oxide units wherein Publication "M02" represents at least one different No. 158348, element ~other than Al or P) present as published tetrahedral oxide units "M02" with charge "n"
October 16, where "n" may be -3, -2, -1, 0 or +1. The 1985 members of thls novel olass o molecular sieve compositions have crys~al framewor~ structures of ~102, P02 amd M02 tetrahedral units and have an empir~cal chemical composition on an anhydrous basis expressed by the formula:

mR: (Mx~lyPz)02 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of B

1 3 1 0~6~
"R" present per mole of (MXAlyPz)02; "M"
represents at least one element capable of forming framework tetrahedral ox$des; and "x", "y" and "z" represent the mole fractions of "M", aluminum and phosphorus, respecti~ely, present as tetrahedral oxides. "M" is at least one different elements ~Ml) such ~hat the molecular sieves contain at leas~ one framework tetrahedral units in additi.on to A102 and PO~. "M" is at leaxt one element selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium and lithium, and when "M" denotes two elements the second element may be one of the aforementioned and/or is at least one element selected from the group consisting of cobalt, iron, magnesium, manganese, titanium and zinc.
The ELAPO molecular sieves are generally referred to hexein by the acronym or "ELAPO" to designate element(s) "~" in a framework of A102, P02 and M02 tetrahedral oxide units. Actual class members will be identified by replacing the "EL" of the acronym with the elements present as M02 tetrahedral units.
When "M" denotes two elements 'IM" may also be at least one element selected from the group consisting of cobalt, iron, magnesium, manganese, titanium and zinc. For example, in each instance "M" includes at least one of the first group of elements, e.g.~ As, Be, etc., and when two or more elements are present, the 6 6 ~
second and further elements may be selected from the first group of elements and/or the second group of elements, as above discussed.
,. The ELAPO molecular sieves have crystalline three-dimensional microporous framework structures of A102, P02 and M02 tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
m~:(MxAlyPz)o2i wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "~" present per mole of (MXAlyPz)02 and has a value of zero to about 0.3; "M" represents at least one element capable of forming framewo~k tetrahedral oxides where "M" is at least one element selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, ~ermanium and lithi~m. When "~" includes an additional element such additional elements "M" may be at least one element selected from the group consisting of cobalt, iron, magnesium, manganese, titanium, and zinc.
Th~ relative amounts of element~s) "M", aluminum and phosphorus are expressed by the empirical chemical formula (anhydrous):

mR: (MxAlyPz)02 1 3 1 066~
where "x", "y" and "z reprresent the mole fractions of said "M", aluminum and phosphorus.
The individual mole fractions of each "M" (of when M denotes two or more elements, M1, M2, M3, etc.) may be represented by "xl", "x2", "x3", etc. wherein "x1 ~ X2 ~ and "X3", and etc. represent the individual mole fractions of elements M1, M2, M3, and etc.
for "M" as above defined. The values of "x "x2", ~X3~, etc. are as defined for "x"
hereinafter, where "x1" + "x2" + "X3"...=
"x" and where xl, x2, X3, etc. are each at least 0.01.
The ELAPO molecular sieves have crystalline three-dimensional microporous framework structures of M02, A10~ and P02 tetrahedral units having an empirical chemical compasition on an anhydrous basis expressed by the formula:

mR:(MXAlyPz)02 wherein "R" represents at least one organic templa~ing agent present in the intracrystalline pore system; "m" represents a molar amount of "R" present per mole of (MXAlyPz)02 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 phosphorus, respectively, present as tetrahedral oxides; said mole fractions "x", 13106~
"y" and "z" being generally defined as within the following values for "x", "y", and "z":
~ Mola Fraction Point x __y_~ ~z +_w) A , 0.02 0.60 0.38 -~ 0.3~ 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 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":
Mole Fraction Point x ~~~~ __y__ (z ~ w) a 0.02 0.60 0.39 b 0.02 0.33 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 0.6~ 0.01 ~LPO's are the basic and simplest of the U.S. Patent crystalline aluminophosphates. They each having No. 4,310,440 a framewor~ structure whose chemical composition expressed in terms of mole ratios of oxides is:
A12O3:1-0~0-2p2os each of said framework structures being microporous in which the pores are uniform and have nominal diameters within the range of about 3 to about 10A, an intracrystalline adsorption 1 3 1 06~
capacity for water at 4.6 ~orr and 24C. of at least 3.5 weight percent, the adsorption and desorption of water being completely reversible while retaining the same essential framework topology in both the hydrated and dehydrated state.

U.S. Pat. No. SENAPSO are guinary and senary molecular 4,741,892, sieves that have framework structures of at European least two elements having tetrahedral oxide Patent Publ. units .. M02n.. and having A102-, P02+
0 158 350, SiO2 tetrahedral oxide units, where "n" is -3, publ. oct. 16, -2, -1, 0 or ~1, and have an empirical chemical 1985 compssition on an anhydrous basis expressed by the formula:
mR:(MWAlxpysiz)o2 wherein "R" represents at least one organic templa~ing agent present in the intracrystalline ~ore system; "m" represen~s the molar amount of "R" presen~ per mole of ~MwAlxPySiz)02 and has a value of from O to about 0.3; "M"
represents at least two elements selected from the group consistin~ of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium, and zinc; "n" is as above defined; and ~w~O "x", "y" and "z" represent the mole fractions of elements "M", aluminium, phosphorus and silicon, respectively, present as tetrahedral oxides, each having a value of at least 0,01.
The publication, at pages 14-15, generally descr~bes seeding reaction mixtures to form the desired product.

1 3 ~ G ~
Zeolitic molecular sieves may be represented by the general formula:
Mex~ ~AlO~)X(si'~)2)Y] ZH20 n where Me is a metal cation, x/n is the number of exchangeable metal cations of valence n, x is also the number of aluminum ions combined in the form of aluminate, y is the number of silicon atoms and z is the number of water molecules, removal of which produces the characteristic pore or channel system. The ratio z/x is a number from 1 to 5, usually from 1 to 2.
Typical of the zeolitic molecular sieves are chabazite, faujasite levynite, Linde Type A, gismondine, erionite, sodalite, Linde Type X and Y, analcime, gmelinite, harmotome, levynite, mordenite, epistilbite, heulandite, stilbite, edingtonite, mesolite, natrolite, scolecite, thomsonlte, brewsterite, laumontite, phillipsite, the ZSM's (e.g..~ ZSM-5~, ZSM-20', ZSM-12~, ZSM-34~, etc.) and Beta' and the like. Typical of suitable zeolitic molecular sieves employable in the practice of this invention are the following:
Zeolites- A, AgX, AgY, AlHY, alkylammonium X and Y, BAX, BaY, BeY, Ca-A, Ca-near faujasite, Ca-HX, Ca-X, Ca-Y, CdX, CdY, CeY, CoA, CoX, CQY, CrY, CsL, CsX, CsY, Cu-X, Cu-Y, Cu-diethylammonium Y, Cu-ethylammonium Y, Fe-X, Fe-Y, group IAX, group IAY, group IIAY, HY, KL, KX, KY, L, La-X, La-Y, LiA, LiX, LiY, LZ-10, LZ-210, MgHY, MgNa, MgNH4Y, MgX, MgY, MnX, MnY, Na-A, Na-near ~aujasite, Na-L, Na-X, Na-Y, NH4L, NH4X, NH4Y, Ni-A, Ni-X, Ni-Y, omega, PdY, phosphate, Pt, rare earth X, rare earth Y, RbX, RhY, SrX, SrY, steam stabilized or 'See U.S. Patent No. 3,207,886.
'See U.S. Patent No. 3,972,983.
~See U.S. Patent No. 3,832,449 ~See U.S. Patent No. 4,079,095.
'See U.S. Patent No. 3,308,069 and U.S. Reissue Patent ' No. 28,341.
37 .

1 31 0~3 ultra stable Y, tetramethylammonium Y, TIX, triethylammonium Y, X, Y, Y-82, ZK-5, Zn-mordenite, Zn-X, An-Y, the ZSMs, supra,~and the like.
Other zeolitic CMSCs useful in the present invention include boron-treated aluminosilicates, such as described in U.S. Patent 4,613,720. Other NZMSs include the silica molecular sieves, such as silicalite as depicted in U.S. Patent No. 4,061,724.
The average diameter of the pores on the presently useful CMSMs is preferably in the range of about 3 angstroms to about 15 angstroms as determined by measurements described in "Zeolite Molecular Sieves" by Donald W. Breck, published by John Wiley ~ Sons, New York, 1974. This average diameter is referred to as the average effective diameter. When the feedstock and desired product or products are relatively small, e.g., organic components containing 1 to about 10 and preferably 1 to about 4 carbon atoms per molecule, the CMSC preferably has small pores.
The presently useful small pore CMSC's are defined as having pores at least a portion, preferably a ma~or portion, of which have an average effective diameter characterized such that the adsorption capacity (as measured by the standard McBain-Bakr gravimetric adsorption method using given adsorbate molecules) shows adsorption of oxygen ~average kinetic diameter of about 0.346 nm) and negligible adsorption of isobutane (average kinetic diameter of about 0.5 nm). More preferably the average effective diameter is characterized by adsorption of xenon (average kinetic diameter of about 0.4 nm) and negligible adsorption of isobutane and most preferably by adsorption of n-hexane (average kinetic diameter of about 0.43 nm) and negligible adsorption of isobutane. Negligible adsorption of a given adsorbate is adsorption of less than three percent by weight of the CMSC and adsorption of the adsorbate is over three percent by weight of the adsorbate based on the weight of the CMSC. Certain of the CMSCs usefu; on the present invention have pores with an average effective diameter in the range of about 3 angstroms to about 5 angstroms.

13~U6Gd The preser.tly useful CI~SCs r;lcy be incorpotc.ted intc a sclia cor.lposition, ~referabl~ solia ~articles, in which t}~e cctalyst is present in an æ~ount eifective to ~rono~e the ~esirec cl~er:!ical ccnveriorl. In one er;boc:ii;ent, the ~-~olic particles co.::rri-e a ccatalytically e~fecti~e al:ount of the cct-l~st and ;atri~; r::ateriai, rreferar~ly at least one of d filler nlateriai na c ~iroer n~terial, to proviac a ^esirec prorpertl~ cr ~ro~erties, e.g., desire catalyst ilutior., r:ecnanical strell~,tl allu the lihe, to the solid con~:};osition. Such matri~ ateriais are ofte to sor.e e~.tent Lorous in na;ure ar.a cf'~rl have SOI:!e nGI-I-~elective cctc.l~tic ~cti~.it- to ~rot:ote the for~ation of unc~e~ire~ pro ucts ana ~I;al or nal r,ot be effecti-~e to L~rol:!ote tile ce_ire c}lel;:ica' conveLsion. For ev.al;ple, aci~ ~ e~ ir. tne ..atrix n:aterial n:c.y r~Lonote non-selective che:ical convercion.
~uch .n~ztri::, e.s., filler ancl binuer~ ?.:caterials incluue, for e.;a.~rle, syr,tile~ic an~ nctuLclll~ occurrirl~ substar.ces, I::etal o~iccs, clays, silicas, aluninas, silica-alu~ lcs~ silica-nlac;nesias, silica-~iLco~lias, silicc.~thoLiac, silica-berylia_, ~ilica-titanizs, silica-al~n~irlt-tilorias, silica-alul;~irla-~irconias, nli.tures of these an~ the like.
Tne solid col:!rosition, e.g., solia particles, preferaDly cvn:prises about 1~ to a~out 59~r n~ore preferai~ly about 5'0 to about 5C% anc still n~ore prefera~ly a~out 10'-~ to abo~lt 80%, L~y weisht o~ CPiSC; and about 1~ to about 35%, nore prefera~ly 3~

1;~1()6~

about 5~ to about 90% and still more preferably about 10% to about 80%, by weight of matrix material.
The preparation of solid compositions, e.g., solid particles, comprising CMSC and matrix material, is conventional and well known in the art and, therefore, need not be discussed in detail here. Certain of such preparation procedures are described in the patents and patent application~ referred to above, ~s well as in U.S. Patents 3,140,253 and RE.27,639. Catalysts which are formed during and/or as part of the methods of manufacturing the solid compositions are within the scope of the present invention.
In one e~bodiment, at least one component of the solid composition, preferably at least a portion of the matrix material component, i8 contacted prior to the feedstock/solid composition contacting to provide a more effective solid composition. In a particular embodiment, at least a portion of the matrix material (or matrix material precursor) is contacted prior to the matrix material being combined in the solid composition.
For example, if the matrix material includes acid sites which can result in non-selective conversion during the feedstock/solid composition contacting, the matrix material, preferably separate and apart, from the CMSC, can be contacted with a basic component, e.g., ammonia and the like, in an amount effective to ,A

) 6 ~ ,3 neutralize at least a portion, preferably a major portion and more preferably substantially all, of the acid sites on the matrix material being contacted. Care should be taken to avoid regeneratin~ these acid sites. After this contacting, the matrix material and CMSC can be combined into the solid composition, e.g., using conventional techniques.
This embodiment provides substantial advantases. For example, the matrix material alone may be contacted at more severe conditions than would be possible if the CMSC was present.
Also, relatively inexpensive basic components, e.g., ammonia and the like, can be employed to contact the matrix material, again with no concern for harming the CMSC which is not present. Of course, this contacting should be conducted so as not to substantially adversely affect the matrix material being contacted, the final composition or the desired chemical conversion.
The solid particles including the CMSC may be of any size functionally suitable in the present invention. In order that the catalyst can be utilized more effectively and if a fixed bed of solid particles is not employed, the solid particles are preferably small relative to fixed bed solid particles used to promote similar chemical conversions. More preferably, the solid particles have a maximum transverse dimension, e,.g., diameter, in I~U6G~3 the range of about 1 micron to about 500 microns, still more preferably about 25 microns to about 200 microns.
The solid particles may be subjected to spray drying as part of the solid particle manufacturing process to form the solid particles or precursors of the solid particles. An additional advantage of employing such spray drying is that the conditions of such step can be controlled so that the product solid particles are of a desired particle size or size range. The use of spray drying in such solid particle manufacturing is conventional and well known, and therefore need not be discussed in detail here.
~ he non-zeolitic molecular sieves or NZMS's are particularly useful in the practice of the present invention. Among the NZMS's, the SAPO's are particularly useful. SAPO-17 and SAP0-34, which is described in detail in Example 38 of U.S. Patent 4,440,871, are especially preferred catalysts for promoting the reaction of molecules containing one carbon atom, e.g., methane, methanol, methyl halide, and the like, to form products containing up to about 6, preferably up to about 4, carbon atoms per molecule, e.g., ethylene, propylene, butylene and the like.
Currently, SAP0-34 is most preferred.
Although the present process may be conducted in the presence of a solid particles/liquid slurry, it is preferred that ! ~ 42 1 3 1 06~

the solid particles be present in ~he fluidized state or as a fixed bed, more preferably in the fluidized state, e.g., as a fluidized bed of solid particles. The use of fluidized solid particles provides improved process control, in particular temperature control and catalytic activity control and/or selectivity control to the desired product.
The chemical conversion or reaction obtained by practicing the present invention can vary widely and depends, for example, on the feedstock and catalyst employed and on the feedstock/catalyst contacting conditions used. Substantially any chemical conversion or reaction which is capable of being catalyzed by a CMSC and conducted in a slurry system may be conducted while practicing the present invention. Examples of reactions which ~ay be obtained include cracking;
disproportionation; olefin production from non-olefin feedstocks;
olefin interconversion; aldol, e.g., aldehyde-aldehyde, ketone-ketone, aldehyde-ketone and aldehyde or ketone-aromatic component, condensation; condensation reactions to produce cyclic lactams, isoprene formation; alkylation (aromatic, e.g., benzene, toluene and phenol alkylation); and isomerization (xylene isomerization). one particularly preferred chemical conversion or reaction involves olefin production from non-olefin feedstocks, more preferably feedstocks comprising aliphatic hetero compounds.

1 3 1 06~

Substantially any feedstock or combination of feedstocks including 1 to about 6 carbon atoms per molecule may be employed in the present invention. The present reaction system is particularly applicable to organic feedstocks containing 1 to about 6 carbon atoms per molecule, preferably having molecules comprising carbon and hydrogen, and more preferably at least one other element. This other element is preferably selected from the group consisting of oxygen, sulfur, halo~en, nitrogen, phosphorus and mixtures thereof, with oxygen being particularly preferred.
The present invention is particularly useful in converting feedstocks having relatively small molecules, i.e., molecules having relatively small kinetic diameters. Thus, the feedstock contains 1 to about 6, preferably 1 to about 4, carbon atoms per molecule. Aliphatic hetero compounds are particularly preferred feedstocks for use in the present invention, especially when light olefins, i.e., olefins containing 2 to about 6 and preferably 2 to 4 carbon atoms per molecule, are to be produced.
When light olefins are the desired product, such olefins are preferably produced as the major hydrocarbon product, i.e., over 50 mole percent of the hydrocarbon product is light olefins. The term "aliphatic hetero compounds" is employed herein to include alcohols, halides, mercaptans, sulfides, amines, ethers and carbonyl compounds (aldehydes, ketones, carboxylic acids and the ' ~ 44 13106~,~

like). The aliphatic moiety preferably contains from 1 to about 10 carbon atoms and more preferably contains from 1 to about 4 carbon atoms. Suitable reactants include lower straight or branched chain alkanols, their unsaturated counterparts, and the nitrogen, halogen and sulfur analogue of such. Representative of suitable aliphatic hetero compounds include: methanol; methyl mercaptan; methyl sulfide; methyl amine; dimethyl ether; ethanol;
ethyl mercaptan; ethyl chloride; diethyl ether; methylethyl ether; formaldehyde; dimethyl ketone acetic acid; n-alkyl amines; n-alkyl halides and n-alkyl sulfides having n-alkyl group having 3 to 6 carbon atoms; and mixtures thereof. In one embodiment, e.gO, where light olefins are the desired products, the feedstock is preferably selected from the group consisting of methanol, ethanol, dimethyl ether, diethyl ether and mixtures thereof, with methanol being particularly preferred.
In certain instances, it is preferred that the feedstock/solid composition contacting conditions be such that the contacting temperature e~ceed the critical temperature of the feedstock. In other words, in certain embodiments, the feedstock is preferably in the supercritical state at the feedstock/solid composition contacting conditions. Having the feedstock in the supercritical state is particularly useful when the feedstock contains 1 to about 4 carbon atoms per molecule.

13 1 06G~

The product or products obtained from the feedstock/solid composition contacting will, of course, dspend, for example, on the feedstock, catalyst and conditions employed. Preferably, the desired product is organic. However, it should be noted that a necessary, and therefore desired, reaction by-product may be inorganic even when the primary product sought is organic. This is exemplified by the conversion of methanol to light olefins plus water. The organic product or products have molecules which preferably include carbon and hydrogen. In one embodiment, the desired product preferably contains 1 to about 6, more preferably 1 to about 4, carbon atoms per molecule. The desired product or products preferably have kinetic diameters which allow such product or products to be removed from or escape from the pores of the CNSC.
In addition to the feedstock, a diluent may be used in conjunction with the feedstock if desired and/or beneficial to the overall process. Such diluent may be mixed or combined with the feedstock prior to the feedstock/solid composition contacting or it may be introduced into the reaction zone separately from the feedstock. Preferably, the feedstock and diluent are both substantially continuously fed to the reaction zone during this con~acting. Such diluent preferably acts to moderate the rate, and possibly also the extent, of feedstock chemical conversion and may also act to aid in temperature control.

1 31 06~

Typical of the diluents which may be employed in the instant process are helium, argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, water, hydrocarbons and mixtures thereof. The diluent, if any, is preferably selected from the group consisting of helium, argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, water and mixtures ~hereof, with water, nitrogen and mixtures thereof, in particular water, being more preferred. The amount of diluent employed, if any, may vary over a wide ranye depending on the particular application involved. For example, the amount of diluent may be in an amount in the range of about 0.1~ or less to about 99% or more of the moles of feedstock.
The feedstock/solid composition contacting step of the present process often results in the CMSC losing at least a portion of at least one desirable property, e.g., catalytic property. The solid composition is preferably contacted with regeneration medium to substantially maintain or improve the effectiveness of the catalyst to promote the desired chemical conversion. For example, the catalyst may become less effective due to formation of carbonaceous deposits or precursors of such deposits in the pores or other parts of the CMSC and/or solid composition during the feedstock/solid composition contacting.
In one embodiment, the regeneration medium acts to reduce the X

1 31 06~

average kinetic diameter of moleculeR present on the pores of the CMSC. Such reduction in the kinetic diameter of these molecules is preferably sufficient to allow the resulting molecules to leave or exit the catalyst pores, thereby providing more pores and/or more volume for the desired chemical conversion. The catalyst is regenerated, such as for example, by removing carbonaceous deposit material by oxidation in an oxygen-containing atmosphere.
In one embodiment, the catalyst and/or solid composition, preferably the catalyst, includes at least one added component effective to promote the action of the regeneration medium. For example, the catalyst may include at least one metal component effecti~e to promote the oxidation of the carbonaceous deposit material. Of course, such metal component should have no substantial ad~erse effect on the desired chemical conversion.
The specific added catalyst component depends on the requirement of the particular application involved. Examples of such added components include components of transition metals, such as nickel, cobalt, iron, manganese, copper and the like; the platinum group metals such as platinum, palladium, rhodium and the like; and the rare earth metals such as cerium, lanthanum and the like, and mixtures thereof. If an added metal component is used, it is preferred that this component be present as a minor ~ ' 48 .

1 31 Oo~

amount, more preferably as about 1 ppm to about 20%, by weight (calculated as elemental metal~ of the weight o~ catalyst employed.
Alternately to the oxidative catalyst regeneration, a reducing medium can be employed to regenerate the catalyst. Such reducing medium, preferably selected from the group consisting of hydrogen, carbon monoxide and mixtures thereof, and in particular hydrogen, can, for example, be used to react with molecules, e.g., of carbonaceous deposit material precursor, in the pores of the catalyst to produce molecules of reduced kinetic diameter so that such produced molecules can exit the pores of the catalyst.
In one embodiment, the reducing medium is hydrogen and the catalyst includes at least one component, preferably a metal component, effective to promote hydrogenation of molecules present on the catalyst, e.g., in the pores of the ~atalyst, at the conditions of the reductive regeneration.
In one embodiment the regenerated solid composition, prior to being used again in the feedstock/solid composition contacting step is subjected to one or more treatments or contactings to condition th~ regenerated solid composition to have increased effectiveness, e.g., increased selectivity to the desired product or products, in the feedstock/solid composition contacting step.
For example, the rPgenerated solid composition ~' ~ 49 . ~
1 31 a6~

can be contacted at an increased temperature relative to the temperature at which the solid composition/regeneration medium contacting takes place and/or in the presence of steam (in the substantial absence of feedstock) in an amount effective to condition the regenerated solid compo6ition to have increased effectiveness in the feedstock/solid composition contacting. The amount of steam employed during this contacting is preferably increased relative to the steam, if any, conventionally used to transfer such solid composition or solid particles from a catalyst regeneration zone to a reaction zone. In one particular embodiment where steam is used as a diluent in the feedstock/solid composition contacting step, the diluent steam is contacted preferably at a temperature increased relative to the regeneration temperature, with the solid composition prior to the feedstock/solid composition contacting to condition the solid particles as described herein. Such hig~ temperature/steam -ontacting often deactivates the solid composition, in particular the matrix material of the solid composition, to some extent and acts to improve the selectivity of the solid composition to the desired product or products. Preferably both high temperatures and steam are employed. Care should be taken to control this contacting to avoid substantial permanent or irreversible damage to the CMSC.

~, . .

~3~Q6~

In one embodiment, the regenerated solid composition is contacted in the presence of at least one component in an amount effective to condition the regenerated solid composition to have increased effectiveness in the feedstock/solid composition contacting~ The component may be inorganic or organic, with organic components being preferred. Such organic components preferably include carbon and hydrogen, and more preferably at least one other element, for example, halogen, nitrogen, oxygen, phosphorus, sulfur and mixtures thereof. Preferably, the component is substantially incapa~le of entering the pores of the CMSC. For example, the component may be dibenzyl benzenes, diphenyl ether and the like and mixtures thereof, particularly if the CMSC has pores with small average effective diameters, i.e., about 5 angstroms or less.
In a particular embodiment, this component is a basic component, more preferably a basic component the molecules of which are substantially preven~ed, e.g., because of size and/or shape considerations, from entering the pores of the CMSC. Such basic component preferably acts to inactivate or reduce the undesired catalytic activity of the matrix material without substantially affecting the desired catalytic activity of the CMSC. The basic material is preferably selected from the group consisting of pyridine, pyridine derivatives, quinoline, ` Xl 1 31 066~

quinoline derivatives and mixtures thereof, particularly when the preferred rela~ively small effective diameter CMSC's are employed. The amount of such basic components or components employed may vary over a wide range, provided that such component is effective to improve the effectiveness of the solid composition. Such basic component is preferably present in an amount in the range of about 0.01% to about ~0%, more preferably about 0.1% to about 15%, by weight of the solid composition.
In another embodiment, the regenerated solid composition is contacted with a feed material, preferably other than the feedstock or the product, at conditions to chemically convert the feed material and condition the regenerated solid composition to have increased effectiveness in the feedstock/solid composition contacting. The chemical conversion of such feed material preferably selectively deactivates the matrix material in the regenerated solid composition. This feed material/solid composition contacting preferably takes place in the substantial absence of the feedstock and the desired product. The feed material, and the product or products of the conversion of the feed material and the feed material/regenerated solid composition contacting conditions should have no substantial detrimental effect on the CMSC, the feedstock and desired product and on the feedstock/solid composition contacting. The feed ~ 52 1 31 a6~, material is preferably selected to be substantially incapable of entering the pores of the CMSC. One particularly preferred class of feed materials is hydrocarbons, more preferably paraffins.
The hydrocarbons employed preferably contain about 3 to about 20, more preferably about 7 to about 20, carbon atoms per molecule.
Preferably, the feed material/regenerated sclid composition contacting takes place at conditions effective to form carbonaceous deposit material, or precursors of such deposit material, on the solid composition. More preferably, the regenerated solid composition after this feed material/regenerated solid composition contacting contains about 0.5% to about 20% by weight of such deposit material and/or precursors of such deposit material. In one specific embodiment, the feed material/regenerated solid composition contacting occurs at conditions to crack the hydrocarbons, e.g., paraffins. Such conditions preferably include temperatures in the range of about 200C to about 600C.
The above-noted embodiments involving subjecting the regenerated solid composition to one or more treatments or contactings to condition the regenerated solid composition to have increased effectiveness in the feedstock/solid composition contacting step can be advantageously utilized to contact the unused or virgin solid composition prior to the initial X ~ 53 !~

1 31 06G~

feedstock/solid composition contacting. Thus, such treatments or contactings of unused or virgin solid compo6ition to condition the solid composition to have increased effectiveness in the feedstock/solid composition contacting step are within the scope of the present invention.
The instant feedstock/solid composition contacting step may be carried out in a single reaction zone or a plurality of such zones arranged in series or in parallel. After the desired product or products are separated from the solid composition using, for example, solid/gas separation devices such as cyclone separators, various techniques, such a distillation, adsorption and the like, can be used to recover or purify such product or products.
The conditions at which the feedstock/solid composition contacting occurs can vary widely depending, for example, on the specific feedstock and CMSC employed, and on the specific product or products desired. The present process is particularly applicable with feedstock/solid composition contacting temperatures in excess of about 200C, more preferably in excess of about 300C, and with pressures in excess of about 10 psig, more preferably in excess of about 50 psig. If light olefins are to be produced from feedstock containing 1 to about 4 carbon atoms per molecule, feedstock, solid composition contacting ~ !

! 54 temperatures are preferably in the range of about 200C to about 600C or even about 700C, more preferably about 350 to about 550C and still more preferably about 400~ to about 500C, with pressures preferably below about 1500 psig.

Two matrix materials, designated Matrix A and Matrix B, were conventionally spray dried into solid particles having an average particle size of about 150-200 microns. Matrix A was composed of 15% by weight of alumina binder and 85% by weight of kaolin clay filler. Matrix B was composed of 25% by weight of alumina binder and 75% by weight of kaolin clay filler.

An experimental apparatus used in Examples 1 to 4 was as follows:

The reactor was a 1 inch O.D. stainless steel fluidized bed reactor with an extended disengagement zone at the top. The reactor had previously been coated internally with sodium silicate to minimize the catalytic activity of the reactor itself. The reactor was loaded with either Matrix A or Matrix B, as desiredO The reactor temperature was controlled by the Techne SBL2-D fluidized sand bath in which the reactor was located.
Analytical grade methanol was feed using a metering pump. The X' 1 31 06~,g methanol was vaporized and preheated in the feed lines to the reactor using heat tape. Methanol flow was measured by periodically timing the level change in a burette on the pump suction line~ A small rotameter was also used to check the methanol flow.

Nitrogen diluent was fed from high pressure cylinders. It was mixed with the methanol upstream of the reactor. When pyridine was fed to the reactor in place of methanol, nitrogen was also fed to the reactor in an amount and at a rate sufficient to maintain the matrix material in a fluidized state. Nitrogen flow was controlled with a Veriflow controller, and measured with a rotameter.

Pressure in the reactor was controlled using a Grove pressure regulator on the reactor ou~let. Pressure was reduced after the reactor outlet to about 5 psig to avoid condensation in the sample lines. From the reactor, steam jacketed lines led to the gas chromatograph, then to the turbine flow meter used for measuring gas flows. Fittings and other potentially cool areas were electrically heated and insulated to prevent any ~ondensation of water or heavy products in the sample lines. The gas stream then went to a condenser, through a wet test meter and was vented hack to a hood.

~ , 56 Regeneration was controlled by a set of low wattage ASC0 solenoid switching valves, which were controlled by an IBM PC
drive ISAAC data acquisition and control system.

A brief series of two (2) experiments was run at substantially constant temperature, pressure, and methanol and nitrogen feedrates. Approximately two (2) minutes into each experiment, the methanol feed to the reactor was stopped, pyridine was substituted for the methanol for a brief time, and then methanol (with no pyridine) wa~ again fed to the reactor.

A second brie~ series of two (20 experiments was run repeating the first series except that a material comprising primarily diphenyl ether, and sold by Dow Chemical Company under the tradename Dowtherm A, was used instead of pyridine.

In each of the first experiments, the system was operated at conditions which would normally (without the substitution of pyridine) give long-term methanol conversion to products other than dimethyl ether of about 7 to 8%. Upon resuming methanol flow after pyridine contacting, methanol conversion immediately dropped to less than 3%. However, as the experiments continued, the methanol conversion gradually recovered to about the previous level. In the second series of experiments, treatment with the diphenyl ether material resulted in a drop in methanol conversion from about 5.6~ to about 4.~%.

X

1 31 06~

Without limiting the present invention to any theory or mechaniæm of operation, it may be as postulated that the pyridine was adsorbed on the surface o~ the matrix material. The pyridine was gradually desorbed during the experiments, exposing the active acid sites of the matrix material again. The relatively large, bulky diphenyl ether molecules ara also adsorbed on, and desorbed from, the surface of the matrix material. The pyridine was more effective than the diphenyl ether in reducing the largely non-selective catalytic activity of the matrix materials because it is basic and can chemically neutralize the acid sites of the matrix material.

The use of such conditioning agents is particularly advantageous when a small pore CMSC is included in solid particles including such matrix materials. The molecules of the conditioning agent are sized, e.g., have kinetic diameters, such that the conditioning agent is substantially prevented from entering the pores of the CMSC. Thus, the conditioning agent effectively reduces the largely non-selective catalytic activity of the matrix material without substantially affecting the CMSC.
Overall, the solid particles are more selective toward promoting the desired chemical conversion of the feedstock, e.g., methanol.

Since the matrix material is often most active at the start of feedstock contacting, it may be desirable to contact the 1 31 Q~3 solid particles with an effective amount of conditioning agent prior to such contacting. When the conditioned solid particles are contacted with the feedstock, ~he solid particles often gradually become deactivated. This gradual deactivation may continue to moderate the non-sel~ctive activity of the matrix material even though the conditioning agent may gradually become disassociated, e.g., desorbed, from the solid particles. In one embodiment, the conditioning agent is fed to the feedstock/solid particles contacting zone or zones, preferably on a substantially continuous basis during such contacting, to maintain a level, preferably a substantially steady-state level of conditioning agent associated, e.g., adsorbed, on the solid particles. Of course, the solid particles can be contacted with conditioning agent prior to the feedstock contacting, and also the conditioning agent can be fed to the feedstock/solid particle contacting zone. The specific conditioning agent employed and the amounts of agent to be employed and the optimum method of employing the conditioning agent are to be chosen based on the specific application to be encountered.

This example illustrates an additional approach to improving the overall catalytic performance of solid particles comprising CMSC and matrix material.

~ 31 06~

A first slurry of 50% by weight SAP0-34 crystals and 50% by weight water is prepared and subjected to continuous mixing.

In a separate vessel, a second, aqueous slurry of kaolin clay and alumina is prepared. Am~onia gas is bubbled through this second slurry until substantially all the acid sites in both the alumina and kaolin clay are neutralized. The first slurry is added to the second slurry to form a combined slurry which is mixed for about 10 minutes. The combined slurry is then stone milled to obtain a substantially uniform particle distribution.

The milled slurry is then spray dried to produce particles having an average particle size of about 70 microns. The spray dried particles are calcined for two houxs at 600C in a nitrogen atmosphere.

The compositions of the first and second slurries are chosen so that the final particles contained 60% by weight SAP0-34, 23%
by weight kaolin clay and 17% by weight alumina.

These solid particles are tested for methanol conversion capacity in the apparatus described above. These solid particles have improved overall selectivity to light olefins relative to similar solid particles in which the matrix material is not contacted with a~monia.

i ~ 60 t 3 1 06~3 This approach to modifying the performance of solid particles i5 advanta~eous because any suitable basic material may be employed. In other words, since the C~SC i8 not present during the basic material/matrix material contacting, there is no need to choose the basic material not to interfere with the pores of the catalyst. Of course, the basic material chosen should have no substantially deleterious effect on the matrix material, the final solid particles or on the desired feedstock conversion.
Also, care should be exercised to inhibit the regeneration of acid sites in the matrix material after such acid sites have been neutralized. In one embodiment, the solid particles prepared by neutralizinq acid sites in the matrix material are advantageously contacted with one or more conditioning agents prior to and/or during the feedstock~solid particle contacting.

This Example illustrates a further additional approach to improving the overall catalytic performance of solid particles comprising CMSC and matrix material.

Solid particles prodused in accordance with Example 5, except that no ammonia contacting is employed, are used. These particles are contacted with dodecane at conditions effective to crack a portion of the dodecane and form carbonaceous deposit 131066~

material on the solid particles. This contacting is continued until the solid particles include about 2% by weight of the carbonaceous deposit material.

These carbonaceous deposit containing material-containing solid particles are tested for methanol conversion capability in the apparatus described above. ~hese solid particles have improved overall selectivity to light olefins relative to similar solid particles which include no carbonaceous deposit material.

A commercially sized fluidized bed reaction system is constructed to produce SOOO barrels per day of mixed ethylene and propylene from methanol. The system includes three reactor vessels in parallel. Each of the reactor vessels are equipped with a number of cyclone separators to aid in removing gases from the reactor vessel while holding the catalyst inside. The system also includes a conventional product handling/separation sub-system to recover and purify the products to the extent desired.

The feed system to each of the reactor vessels includes a separate steam inlet. Steam is substantially continuously fed to each of the vessels. A valved methanol inlet and a valved air inlet are also provided to each of the vessels. The methanol and air inlets are controlled so that only one of methanol or air is fed to any one reactor vessel at any one time.

X I

1 31 06~3 Each of these reactor vessels are operated on the following reaction/regeneration cycle. Solid particles, similar in composition to that prepared in Example 5, are placed in the reaction vessel and heated to a temperature of 500C. Pyridine is combined with the steam and fed to the vessel for a time sufficient to neutralize a major portion of the acid sites in the matrix material of the solid particles. Vaporized and heated methanol is fed to the vessel (along with the pyridine and the steam diluent) to produce light olefins which are removed from the vessel through the cyclone separators. Throughout the cycle the catalyst is maintained at a temperature of about 500~C. and a pressure of about 80 psig. After a period of time, methanol flow and pyridine flow is stopped and steam purges the vessel of methanol. After the purge, air is introduced into the reactor vessel to regenerate the catalyst. After the desired catalyst regeneration, the flow of air is stopped and steam purges the vessel of air. At this point, the cycle is begun again. The time sequencing of this cyclic operation is such that no less than two of the reactor vessels operate in the reaction mode at any one time.
This cyclic operation is effective in producing ethylene and propylene, in particular ethylene, from methanol.
While the present invention has been described I 3 ~ 0~63 with respect to various specific examples and embodiments, it is to be understood that the invention is not limited thereto and that it can be variously practiced within the scope of the following claims.

Claims (64)

1. In a process for converting a feedstock containing 1 to about 6 carbon atoms per molecule which includes (a) contacting said feedstock with a solid composition comprising a crystalline microporous three dimensional solid catalyst having the ability to promote said conversion, and matrix material at conditions effective to convert said feedstock, to produce at least one desired product, and to at least partially deactivate said solid composition; (b) contacting said deactivated solid composition with regeneration medium at conditions to at least partially regenerate said solid composition; and (c) repeating step (a), the improvement which comprises (d) contacting said regenerated solid composition prior to step (c) to condition said regenerated solid composition to have increased effectiveness in step (c).

2. The process of claim 1 wherein step (d) is conducted in the presence of at least one component in an amount effective to condition said regenerated solid composition to have increased effectiveness in step (c).

3. The process of claim 1 wherein step (d) is conducted in the presence of steam in an amount effective to condition said regenerated solid composition to have increased effectiveness in step (c),

4. The process of claim 1 wherein step (d) is conducted at an increased temperature relative to the temperature at which step (b) is conducted.

5. The process of claim 4 wherein step (d) is conducted in the presence of at least one component in an amount effective to condition said regenerated solid composition to have increased effectiveness in step (c).

6. The process of claim 1 wherein step (d) is conducted in the presence of at least one basic component in an amount effective to condition said regenerated solid composition to have increased effectiveness in step (c).

7. The process of claim 6 wherein said basic component is substantially capable of entering said pores of wqie catalyst.

8. The process of claim 1 wherein step (d) comprises contacting said regenerated solid composition with a feed material at conditions to chemically convert said feed material.

9. The process of claim 8 wherein said feed material is other than said feedstock.

10. The process of claim 9 wherein said feed material is organic.

11. The process of claim 10 wherein said conditions at which step (d) is conducted are effective to crack said feed material.

12. The process of claim 10 wherein said feed material is paraffinic.

13. The process of claim 10 wherein-said feed material contains about 3 to about 20 carbon atoms per molecule.

14. The process of claim 1 wherein said pores of said catalyst are substantially uniform in size.

15. The process of claim 1 wherein said catalyst is a small pore catalyst.

16. The process of claim 14 wherein said pores have average effective diameters of less than 5 angstroms.

17. The process of claim 1 wherein said catalyst is selected from the group consisting of layered clays, zeolitic molecular sieves, non-zeolitic molecular sieves and mixtures thereof.

18. The process of claim 1 wherein said catalyst is selected from the group consisting of non-zeolitic molecular sieves and mixtures thereof.

19. The process of claim 1 wherein said catalyst is selected from the group consisting of silicoaluminophosphates and mixtures thereof.

20. The process of claim 1 wherein said catalyst is in the range of about 1 to about 99% by weight of said solid composition and said matrix material is in the range of about 1 to about 99% by weight of said solid composition.

21. The process of claim 1 wherein said matrix material includes at least one of (1) a filler material, and (2) a binder material.

22. In a process for converting a feedstock containing 1 to about 6 carbon atoms per molecule which includes (a) contacting said feedstock with a solid composition comprising a small pore crystalline microporous three dimensional, catalyst having the ability to promote said conversion, and matrix material at conditions effective to convert said feedstock, to produce at least one desired product, and to at least partially deactivate said solid composition; (b) contacting said deactivated solid composition with regeneration medium at conditions effective to at least partially regenerate said solid composition and (c) repeating step (a); the improvement which comprises (d) contacting at least one component of said solid composition prior to step (a) to provide said solid composition with increased effectiveness in step (a).

23. The process of claim 22 wherein said solid composition is contacted in step (d).

24. The process of claim 22 wherein step (d) is conducted in the presence of at least one added component in an amount effective to condition said regenerated solid composition to have increased effectiveness in step (a).

25. the process of claim 22 wherein step (d) is conducted in the presence of steam in an amount effective to condition said solid composition to have increased effectiveness in step (a).

26. The process of claim 22 wherein step (d) is conducted at increased temperature relative to the temperature at which step (b) is conducted.

27. The process of claim 22 wherein step (d) is conducted in the presence of at least one basic component in an increased effectiveness in step (a).

28. The process of claim 27 wherein said basic component is substantially incapable of entering said pores of said catalyst.

29. The process of claim 22 wherein step (d) comprises contacting said solid composition with a feed material at conditions to chemically convert said feed material.

30. The process of claim 29 wherein said feed material is other than said feedstock.

31. The process of claim 30 wherein said feed material is organic.

32. The process of claim 31 wherein said conditions at which step (d) is conducted are effective to crack said feed material.

33. The process of claim 31 wherein said feed material is paraffinic.

34. The process of claim 31 wherein said feed material contains about 3 to about 20 carbon atoms per molecule.

35. The process of claim 22 wherein said pores of said catalyst are substantially uniform in size.

36. The process of claim 28 wherein said pores of said catalyst are substantially uniform in size.

37. The process of claim 22 wherein said pores have average effective diameters of less than 5 angstroms.

38. The process of claim 22 wherein said catalyst is selected from the group consisting of layered clays, zeolitic molecular sieves, non-zeolitic molecular sieves and mixtures thereof.

39. The process of claim 22 wherein said catalyst is selected from the group consisting of non-zeolitic molecular sieves and mixtures thereof.

40. The process of claim 22 wherein sad catalyst is selected from the group consisting of silicoaluminophosphates and mixtures thereof.

41. The process of claim 22 wherein said catalyst is in the range of about 1 to about 99% by weight of said solid composition and said matrix material is in the range of about 1 to about 99% by weight of said solid composition.

42. The process of claim 22 wherein said matrix material includes at least one of (1) a filler material, and (2) a binder material.

43. The process of claim 42 wherein step (d) is conducted by contacting at least a portion of said matrix material prior to said matrix material being combined in said solid composition.

44. The process of claim 43 wherein step (d) is conducted in the presence of at least one component in an amount effective to provide said solid composition with increased effectiveness in step (a).

45. The process of claim 45 wherein said component is a basic component.

46. In a process for converting a feedstock containing 1 to about 6 carbon atoms per molecule which includes contacting said feedstock with solid particles comprising a small pore crystalline microporous three dimensional solid catalyst having the ability to promote said conversion and matrix material, said solid particles being present in the fluidized state or in a fixed bed, at conditions effective to convert said feedstock and to produce at least one desired product, the improvement which comprises conducting said contacting in the presence of at least one added conditioning agent in an amount effective to improve the performance of said solid particles in said contacting, said conditioning agent being substantially incapable of entering the pores of said catalyst.

47. The process of claim 46 wherein said solid particles are present in the fluidized state.

48. The process of claim 46 wherein said conditioning agent is effective to improve the selectivity of said solid particles to produce said desired product.

49. The process of claim 46 wherein said conditioning agent is a basic material.

50. The process of claim 49 wherein said basic maternal is selected from the group consisting of pyridine, pyridine derivatives, quinoline, quinoline derivatives and mixtures thereof.

51. The process of claim 46 wherein aid catalyst is in the range of about 1 to about 99% by weight of said solid particles and said matrix material is in the range of about 1 to about 99% by weight of said solid particles.

52. The process of claim 46 wherein said pores of said catalyst are substantially uniform in size.

53. The process of claim 50 wherein said pores of said catalyst are substantially uniform in size.

54. The process of claim 52 wherein said pores have average effective diameters of less than 5 angstroms.

55. The process of claim 46 wherein said catalyst is selected from the group consisting of layered clays, zeolitic molecular sieves, non-zeolitic molecular sieves and mixtures thereof.

56. The process of claim 46 wherein said catalyst is selected form the group consisting of non-zeolitic molecular sieves and mixtures thereof.

57. The process of claim 46 wherein said catalyst is selected from the group consisting of silicoaluminophosphates and mixtures thereof.

58. The process of claim 46 wherein said matrix material includes at least one of (1) a filler material, and (2) a binder material.

59. The process of claim 1 wherein said feedstock is selected from the group consisting of methanol, ethanol, dimethyl ether and mixtures thereof.

60. The process of claim 59 wherein said desired product is selected from the group consisting of ethylene, propylene, butylenes and mixtures thereof.

61. The process of claim 22 wherein said feedstock is selected from the group consisting of methanol, ethanol, dimethyl ether and mixtures thereof.

62. The process of claim 61 wherein said desired product is selected from the group consisting of ethylene, propylene, butylenes and mixtures thereof.

63. The process of claim 46 wherein said feedstock is selected from the group consisting of methanol, ethanol, dimethyl ether and mixtures thereof.

64. The process of claim 63 wherein said desired product is selected from the group consisting of ethylene, propylene, butylenes and mixtures thereof.