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Publication numberCA2319788 C
Publication typeGrant
Application numberCA 2319788
PCT numberPCT/US1999/002379
Publication date20 Nov 2007
Filing date3 Feb 1999
Priority date13 Feb 1998
Also published asCA2319788A1, EP1054732A1, EP1054732A4, US5925330, WO1999041013A1
Publication numberCA 2319788, CA 2319788 C, CA 2319788C, CA-C-2319788, CA2319788 C, CA2319788C, PCT/1999/2379, PCT/US/1999/002379, PCT/US/1999/02379, PCT/US/99/002379, PCT/US/99/02379, PCT/US1999/002379, PCT/US1999/02379, PCT/US1999002379, PCT/US199902379, PCT/US99/002379, PCT/US99/02379, PCT/US99002379, PCT/US9902379
InventorsWieslaw Jerzy Roth
ApplicantMobil Oil Corporation, Wieslaw Jerzy Roth
Export CitationBiBTeX, EndNote, RefMan
External Links: CIPO, Espacenet
A method of modifying a crystalline molecular sieve material
CA 2319788 C
Abstract
There is provided a method for modifying a crystalline molecular sieve material which contains a templating surfactant. The method comprises the step of contacting the crystalline molecular sieve material with a treatment composition which comprises a functionalizing agent, an exchanging moiety and a solvent capable of dissolving the exchanging moiety and the functionalizing agent. The contacting step modifies the crystalline molecular sieve material by functionalizing the molecular sieve material and concurrently removing the templating surfactant from the crystalline molecular sieve material.
Claims(12)
1. A method for modifying a crystalline molecular sieve material which contains a templating surfactant which comprises the step of contacting the crystalline molecular sieve material with a treatment composition which comprises a functionalizing agent, an exchanging moiety and a solvent capable of dissolving the exchanging moiety and the functionalizing agent, the contacting step modifying the crystalline molecular sieve material by functionalizing the molecular sieve material and concurrently removing the templating surfactant from the crystalline molecular sieve material.
2. The method of Claim 1, wherein the crystalline molecular sieve material comprises an inorganic, porous, non-layered crystalline phase material exhibiting, after calcination and/or functionalization, an X-ray diffraction pattern with at least one peak at a d-spacing greater than 18 Angstrom Units with a relative intensity of 100 and having a benzene adsorption capacity of greater than 15 grams benzene per 100 grams anhydrous crystal at 50 torr and 25C.
3. The method of Claim 1, wherein the solvent is selected from alcohols, ethers, amines, halogenated hydrocarbons, carboxylic acids or aromatic, aliphatic ethers or mixtures thereof.
4. The method Claim 1, wherein the solvent comprises an isotropic mixture of at least two components.
5. The method of Claim 1, wherein the functionalizing agent comprises M' X' Y'n~ wherein:
M' is selected from Periodic Table Groups IIA, IIIA, IVA, VA, VIA, VIIIA, IB, IIB, IIIB, IVB, VB or VIB;
X' is selected from halides, hydrides, alkoxyides of 1 to 6 carbon atoms, alkyl of 1 to 18 carbon atoms, alkenyl of 1 to 18 carbon atoms, aryl of 1 to 18 carbon atoms, aryloxide of 1 to 18 carbon atoms, sulfonates, nitrates or acetates;
Y' is selected from the substituents described for X', amines, phosphines, sulfides, carbonyl or cyanos; and n=1-5.
6. The method of Claim 5, wherein M' X' Y'n is selected from chromium acetate, chromium nitrate, tetraethylorthosilicate, tetramethylorthosilicate, titanium tetraethoxide, aluminum isopropoxide, aluminium di-isopropoxide acetoacetic ester chelate, aluminium tri-secbutoxide, aluminum nitrate, Zr-hydroxychloride, cerium nitrate, hexamethyldisilazane, di-secbutoxyaluminoxytriethoxysilane, diethylphosphatoethyl-triethoxy-silane, trimethyborate, chlorodimethylalkylsilane wherein alkyl is C1-18, ammonia-borane, borane-tetrahydrofuran, dimethylsulfidedibromoborane or mixtures thereof.
7. The method of Claim 1, wherein the functionalizing agent is in an amount from 0.01% to 60% by weight.
8. The method of Claim 7, wherein the functionalizing agent is in an amount from 1.0% to 30.0% by weight.
9. The method of Claim 1, wherein the exchanging moiety is selected from mineral acid salts, ammonium salts, quaternary ammonium salts or a functionalizing agent capable of being a cation donor.
10. The method of Claim 1, wherein the exchanging moiety is in an amount from 0.1% to 50% by weight.
11. The method of Claim 10, wherein the exchanging moiety is in an amount from 1.0% to 25.0% by weight.
12. The method of Claim 1, wherein the templating surfactant is selected from cetyltrimethylammonium, myristyltrimethylammonium, decyltrimethylammonium, cetyltrimethylphosphonium, octadecyltrimethylphosphonium, benzyltrimethylammonium, cetylpyridinium, dodecyltrimethylammonium, or dimethyldidodecylammonium.
Description  (OCR text may contain errors)

A METHOD OF MODIFYING A CRYSTALLINE
MOLECULAR SIEVE MATERIAL

This invention relates to a method of modifying ultra-large pore crystalline materials useful as catalysts and sorbents. More specifically, this invention relates to a method of incorporating functional groups into the crystalline material and concurrently recovering a templating surfactant useful in the synthesis of the ultra-large pore crystalline materials.
Porous inorganic solids have found great utility as catalysts and separation media for industrial applications. These materials are commonly synthesized by using organic cationic templates in the synthesis mixture. The use of surfactants as organic templates provides porous solids with ultra large pores up to 100 Angstroms. The cost of these templating surfactants in many instances represents a major fraction of the overall cost of the molecular sieve. One method of removing the templating surfactants from the pores of the freshly synthesized molecular sieve material is to subject the as-synthesized molecular sieve to high temperatures in a controlled oxygen-containing atmosphere to slowly burn off the residual organic template. This step is commonly referred to in the art of molecular sieve synthesis as calcining. Unfortunately, calcining destroys the templating surfactant.
Moreover, the calcined molecular sieve can be more deformed and/or partially collapsed due to shrinkage caused by high calcination temperatures. Inorganic cations may be removed, either before or after calcining, from the as-synthesized molecular sieve by aqueous ion exchange.
However, aqueous ion-exchange techniques have proven largely ineffective for removing the organic templating surfactants from layered and other controlled pore synthetic materials. It would, therefore, be highly desirable to provide a method for the removal and recovery of the templating surfactant which would also preserve the integrity of the molecular sieve.
The porous materials in use today can be sorted into three broad categories using the details of their microstructure as a basis for classification. These categories are 1) amorphous and paracrystalline supports, 2) crystalline molecular sieves and 3) modified layered materials, and have been described in detail in U.S. Patent Nos. 5,145, 816 and 5,143, 879.
One particular area of interest involves anchoring or incorporating functional groups into ultra-large pore crystalline materials in order to engineer unique catalytic sites and/or to tailor the pore size as desired. U.S. Patent No. 5,145,816 describes functionalization of ultra-large pore crystalline materials as-synthesized or after removal of the templating surfactant by calcination. It has been found that the structure of calcined ultra-large pore crystalline materials are more deformed and/or partially collapsed due to structure contraction during calcination. As a result, heat calcined ultra-large pore crystalline materials provide fewer silanol groups available for anchoring functionalizing moieties. Moreover, during removal of templating surfactant by calcination the surfactant is bumed off, thus being effectively destroyed. On the other hand, the use of uncalcined, surfactant containing ultra-large pore crystalline material is undesirable because expensive templating surfactant is left in the as-synthesized structure of the ultra-large pore crystalline materials. Moreover, some templating surfactants fill the pores of the as-synthesized molecular sieve, and must be removed to provide access to the pores for catalysis or sorption.
U.S. Patent No. 5,143,879 teaches a method of recovering organic templates used to synthesize molecular sieves useful as catalysts and sorbents. The method described in the '879 patent requires elevated temperatures, is applied to non-functionalized ultra-large pore crystalline materials, and may provide low recovery yields of removed template at room temperature.
Thus, in light of existing technologies for recovery of templating materials and functionalization of synthetic molecular sieves, such as those discussed above, there exists an ongoing need to develop new and useful catalysts and separation media for industrial applications, which are inexpensive and of considerable benefit from the standpoint of processing.
Accordingly, it is an object of the present invention to provide a method for functionalizing ultra-large pore crystalline material concurrently with recovery of high yields of templating surfactant.
In accordance with the present invention, there is provided a method for modifying a crystalline molecular sieve material which contains a templating surfactant which comprises the step of contacting the crystalline molecular sieve material with a treatment composition which comprises a functionalizing agent, an exchanging moiety and a solvent capable of dissolving the exchanging moiety and the functionalizing agent, the contacting step modifying the crystalline molecular sieve material by functionalizing the molecular sieve material and concurrently removing the templating surfactant from the crystalline molecular sieve material..
The crystalline molecular sieve material preferably includes an inorganic, porous, non-layered crystalline phase material exhibiting, after calcination and/or functionalization, an X-ray diffraction pattern with at least one peak at a d-spacing greater than 18 Angstrom units with a relative intensity of 100 and having a benzene adsorption capacity of greater that 15 grams benzene per 100 grams anhydrous crystal at 50 torr and 25 C.
The treatment composition preferably includes a functionalizing agent, namely M' X' Y',,, wherein:
M' is selected from a group consisting of Periodic Table Groups IIA., IIIA, IVA, VA, VIA, VIIIA, IB, IIB, IIIB, IVB, VB and VIB;
X' is selected from a group consisting of halides, hydrides, alkoxides of I to carbon atoms, alkyl of I to 6 carbon atoms, alkenyl of I to 6 carbon atoms, aryl of 1 to 6 carbon atoms, aryloxide of I to 6 carbon atoms, sulfonates, nitrates and acetates;

Y' is selected from a group consisting of the substituents described for X', amines, phosphines, sulfides, carbonyl and cyanos; and n=1-5.
The exchanging moiety is preferably a cation donor selected from the group of mineral acid salts, ammonium salts, quaternary ammonium salts or a functionalizing agent capable of being a cation donor. Useful templating surfactants include the group consisting of cetyltrimethylammonium, myristyltrimethylammonium, decyltrimethylammonium, cetyltrimethylphosphonium, octadecyltrimethylphosphonium, benzyltrimethylammonium, cetylpyridinium, dodecyltrimethylammonium, and dimethyldidodecylammonium.
Solvents useful for the method of the present invention include alcohols, ethers, amines, halogenated hydrocarbons, carboxylic acid and aromatic or aliphatic ethers.
In one embodiment, the crystalline molecular sieve material of the present invention includes an inorganic, porous crystalline phase material having a hexagonal arrangement of uniformly-sized pores at least 13 Angstrom units in diameter and exhibiting, after calcination, a hexagonal electron diffraction pattern that can be indexed with a dioo value greater than 18 Angstrom Units. The crystalline molecular sieve material useful in the present invention may have a composition expressed as follows:
MWq(W.XbY.ZaOe) wherein M is one or more ions; n is the charge of the composition excluding M
expressed as oxides; q is the weighted molar average valence of M; n/q is the number of moles or mole fraction of M; W is one or more divalent elements; X is one or more trivalent elements; Y is one or more tetravalent elements; Z is one or more pentavalent elements; a, b, c, and d are mole fractions of W, X, Y, and Z, respectively; h is a number of from 1 to 2.5; and (a+b+c+d)=1.
As a result of the present invention a novel, cost-effective method is provided for functionalizing as-synthesized ultra large pore zeolites and concurrently recovering a majority of their templating surfactants. In the method of the present invention removal of surfactant prior to final calcination is cost effective, makes the calcination process more manageable and provides zeolites with higher content of silanol groups which are available for anchoring of functionalizing moieties.
The method of modifying crystalline molecular sieves and simultaneously removing a templating surfactant found in their as-synthesized state is applicable to a wide range of functional groups and templating surfactants.
A preferred ultra large molecular sieve useful in the method of the present invention is M41 S. The preparation and characterization of the ultra large pore synthetic molecular sieves of the present invention are disclosed in U.S. Patent Nos. 5,102,643 and 5,057,296. Certain forms of M41 S are described in U.S. Patent Nos. 5,098,684 and 5,198,203.
The method of the invention takes advantage of a high concentration of hydroxyl groups present in as-synthesized silica based M41 S and other forms of M41 S.
Silicious M41 S

and MCM-41 are preferred due to convenience, cost, ease of preparation and product quality as judged based upon the number of X-ray diffraction peaks observed (e.g., 3-4 for MCM-41).
Silicious M41 S and MCM-41 also have a very high silanol concentration which is available for anchoring functionalizing moieties.
The method of the present invention uses the reaction of hydroxyl groups with a treatment composition comprising M' X' Y'. to anchor or incorporate functionalizing groups into the ultra large porous material of the invention. Functionalizing groups can provide unique catalytic sites within the pores of synthetic molecular sieves or can act as pore size reducing agents so that the pore size can be tailored as desired.
Functionalizing groups may also serve to modify the activity of catalytic sites already present in the molecular sieve material. Functionalizing groups can also serve as precursors to ceramic materials.
Functionalizing Group A functionalizing group will be understood to be a characteristic reactive, covalently or ionically bonded group of a chemical compound and functionalization will be understood to be the incorporation of covalently or ionically bonded functional groups into the molecular sieve material. The functionalizing group of the present invention includes any moiety that is soluble in the extracting solvent, such as alcohol, and can bind to a silanol group.
The functionalization reaction may be described according to the formula Si-O-R + M' X'Y' ----> SiOM' Y' + R' X' wherein Si-O-R' is a site in the lattice of the crystalline material.
R can be H+ or R4N' which is the organic cation specified in the crystallization methods herein described.
M' can be elements of Groups IIA, IIIA, IVA, VA, VIA, VIIIA, IB, IIB, IIIB, IVB, VB, or VIB of the Periodic Table of the Elements, (Sargent-Welch Scientific Co. Cat. No. S-18806, 1979). Preferred elements for M' are Groups IVA, VIA, VIIIA, IIIB and IVB, and most preferred elements for M' are titanium, zirconium, chromium, iron, cobalt, nickel, boron, aluminum, and all lanthanides.
X' can be halides, hydrides, alkoxides of 1-6 carbon atoms, alkyl of 1-18 carbon atoms, aryl of 1-18 carbon atoms, acetates, aryloxides of 1-18 carbon atoms, sulfonates and nitrates. Preferred substituents for X' are halides, alkoxides of 1-6 carbon atoms and acetates.
Y' can be selected from the substituents described for X' , or amines, phosphines, sulfides, carbonyls and cyanos. Preferred substituents for Y' are those described for X', amines, sulfides and alkyls with 1-18 carbon atoms. Most preferred substituents for Y' are those described for X', amines and alkyls with 1-18 carbon atoms; n = 1-5.
Nonlimiting examples for M' X' Y' include chromium acetate, chromium nitrate, tetraethylorthosilicate, tetramethylorthosilicate, titanium tetraethoxide, aluminum isopropoxide, aluminum tri-sec butoxide, aluminum di-isopropoxide acetoacetic ester chelate, hexamethyldisilazane, di-sec-butoxyaluminoxytriethoxysilane, diethylphosphatoethyl-triethyoxysilane, trimethylborate, chlorodimethylalkylsilane wherein alkyl has 1-18 carbon atoms, ammonia-borane, borane-tetrahydrofuran and dimethylsulfide-dibromoborane.
The treated crystalline molecular sieve material can be used as is or may be further subjected to a thermal treatment or treatment with a reactive gas such as oxygen or carbon 5 monoxide for activation.
The treated crystalline material may be described as having functionalizing groups within it according to the formula:

I
-SiOM'Y'
I

These functionalized sites may be, for example:

II
-SiOP(OMe)2, -SiOB(OMe)2, -SiOB(Br)2 = SMe2, -SiOTi(OEt)3, -SiOCr(acetate)2, -SiOCr(nitrate)2, -SiOSi(OMe)3, -SiOA1(s-OPr)2, -SiOA1(s-OBu)2, -SiOSi(OEt)3, OEt 0 O-s-Bu 1 II
-SiOAI -SiOSi-CH2-CH2-P(OEt)2i OSi(OEt)3, I
OEt -SiOSi(CH3)3, -SiOSi(CH3)2C6H13, -S1OS1(CH3)2C18H37, -SiOSi(CH3)2C6H5.

Me=CH3, Et=C2Hs, Pr=C3H7, Bu=C4H9 In these examples, -Si represents a site in the lattice of the crystalline material. Two additional bonds on the Si are not shown. The invention is not limited to the above listed functionalized sites.
The method of the present invention also includes removal of the templating surfactant found in as-synthesized ultra large porous material of the invention. Most importantly, the functionalizing of the ultra large porous material and the removal of the templating surfactant occur concurrently in a one-step method thereby providing a cost effective and efficient manner of recovering and recycling the more expensive component of the functionalized catalyst or sorbent formed by the method of the present invention.

Templating Surfactants As used herein, a templating surfactant refers to an organic templating or directing agent found in the as-synthesized ultra large porous material of the present invention. For a discussion of zeolite directing agents, see R. Szostak's book entitled "Molecular Sieves, Principles of Synthesis and Identification" 79 (1989).
Templating surfactants substantially fill pores of as-synthesized molecular sieves, and must be removed to provide access to the pores for catalysis or sorption. A
nonlimiting list of bulky organic bases which are favored as templating surfactants include cetyltrimetyl-ammonium (CTMA), myristyltrimethylammonium (Ci4TMA), decyltrimethylammonium, cetyltrimethylphosphonium, octadecyltrimethylphosphonium, benzyltrimethylammonium, cetylpyridinium, dodecyltrimethylammonium, and dimethyldidodecyclammonium, merely to name a few. The templating action of various organic entities is also discussed in A. Dyer "An Introduction to Zeolite Molecular Sieves" 60 (1988), as well as in B.M. Lok et al., "The Role or Organic Molecules in Molecular Sieve Synthesis" 3 Zeolites 282 (1983).
Extraction Solvents The extraction solvent of the invention is a treatment composition which is suitable to solubilize at least one exchanging moiety, preferably a cation donor and one functionalizing group which may be the same moiety as the exchanging moiety. Solvents which have the required properties include both aromatic as well as aliphatic ethers (e.g., tetrahydrofuran), alcohols, amines, halogenated hydrocarbons, carboxylic acids and other polar solvents. The exchanging moiety can be provided by inorganic acids or salts, such as ammonium salts. In a preferred embodiment, the water content of the extraction solvent is relatively low only to the extent that facilitates solubilization of the exchanging moiety and/or functionalizing group.
Most preferably the extraction solvent is substantially free of water. The most preferred solvent is an alcohol such as ethanol.
The efficiency of extraction of a templating surfactant from the as-synthesized material is believed to be related to several factors. While not to limit the invention by a recitation of theory, one of the most important factor appears to be the ability of the solvent used for the extraction to solubilize the template or its salt, to interact favorably with the surface and to disrupt oleophilic interactions between moieties of templates with each other and with the surface of the material.
Moreover, the solvent must also have the ability to solubilize the functionalizing group and the exchanging moiety.
Extraction solvents useful for the method of the invention include: methanol, ethanol, benzene, toluene, heptene, diethylether, chloroform, tricholoroethylene, heptene/ethanol (52/48 wt/wt).
It has been found that these solvents can, in some instances, be made even more effective by adding co-solvents such as aliphatic or aromatic hydrocarbons.
Most preferred are solvents which boil below 150 C. Particularly, solvents which boil below 150 C have been found to facilitate both recovery of the templating surfactant as well as recycle of the solvent.
In accordance with the present invention, it has been found that certain isotropic solvent mixtures having a particular set of the solubility, hydrophilic and oleophilic properties, are usually effective for extracting organic surfactants from an as-synthesized zeolite. Alcohols are particularly preferred for forming isotropic solvent mixtures.
Isotropic solvent mixtures useful as extraction solvents in the method of the present invention include the following: hexane/methanol (73/27); hexane/ethanol (73/27); hexaneln-propanol (96/4); heptene/methanol (48/52); heptene/ethanol (52/48); heptene/n-butanol (82/18); cyclohexane/isopropyl (67/33); benzene/methanol (60/40);
benzene/ethanol (68/32);
toluene/methanol (72/28); toluene/ethanol (68/32); trichlorethylenelmethanol (64/36);
trichlorethylene/ethanol (73/27).
Exchanging Moiety To complete the process of extraction of the templating surfactant, it is essential that an exchanging moiety, preferably a cation donor, be available in the treatment composition.
The cation donor can replace the ionic interactions of the surfactant with the hydroxyl groups on the surface. Thus, a cation donor is required which is readily soluble in the treatment composition of the present invention. For example, as shown in Examples 38 and 39 of U.S.
Patent No. 5,143,879 in an organic solution in the absence of a cation donor no extraction of the templating surfactants could take place.
If the functionalizing group is not itself cationic the most preferred cation donors are ammonium salts, quaternary ammonium salts, and quaternary amine salts. Proton donors such as mineral acid are less desirable because protons are likely to compete favorably with the functionalizing group for the anchoring site.
Addition of the cation donor in accordance with the present invention improves template recovery and is believed to preserve hydroxyl content. It is believed that such preservation of hydroxyl content results in the observed improvement in ion exchange and chemical bonding of materials prepared in accordance with the present invention when compared with materials which have been calcined to remove the organic directing agent.
The ratio of treatment composition to treated crystalline molecular sieve material, duration of treatment and temperature are not critical and may vary within wide limits. The temperature may be, for example, from -70 C to 250 C, with from 0 C to 150 C
being preferred and 25 C to 100 C being most preferred. The time may be from 0.1 to 100 hours, with from 0.1 to 30 hours preferred and from 0.1 hours to 24 hours most preferred.
Preferably, the functionalizing agent is present in an amount from 0.01% to 60% by weight, preferably from 1.0% to 30.0% by weight of the treatment composition and the exchanging moiety is in an amount from 0.1% to 50% by weight, preferably from 1.0% to 25.0% by weight of the treatment composition.

It has been found that whenever a functionalizing agent is an ionic compound, then the particular functionalizing agent also acts as cation donor useful to ion exchange the surfactant.
In that case, it is important that the extraction solvent is a polar organic solvent, preferably alcohol. Inorganic polar solvents, such as water, cannot generally be used by themselves to remove templating surfactants. For example, attempts to utilize water as an extraction solvent have yielded poor results (see Example 7). It has also been found that whenever the functionalizing agent is a nonionic compound, then it is important that the extracting solvent is a polar organic solvent, preferably alcohol, which also contains a cation donor, preferably a proton precursor. For example, certain metal containing functional groups, such as those io containing a lanthanide can also serve as the cation donor for recovering the templating surfactant. If the functionalizing agent is neutral such as an alkoxide, then the extraction solvent should include another cation donor such as ammonium acetate.
The invention will now be more particularly described with reference to the following examples, in which percentages are by weight unless otherwise indicated.

In this example, siliceous MCM-41, an ultra large pore crystalline material was prepared. 170 grams of Ultrasil precipitated silica, 200 grams of 25%
tetramethylammonium hydroxide (TMA-OH) and 600 grams of water were reacted at 100 C for one hour.
Subsequently, 375 grams of a 37% solution of dodecyltrimethylammonium chloride (DTMA-Cl) was added to the resulting mixture and was reacted at 150 C for twenty hours.
The resulting solid product was recovered by filtration and dried in air at 110 C . The X-ray diffraction pattern of the as-synthesized product exhibited a three-peak hexagonal pattern of MCM-41 with d-spacing of the first line at 37 Angstrom units as described in U.S.
Patent No. 5,098,684. Similarly, after calcination, a three-peak X-ray diffraction pattern indicative of MCM-41(36), wherein the number in parentheses is the d-spacing of the first line in X-ray pattern was obtained. The as-synthesized product had the following percent by weight composition: 41% ash (essentially, all silica), 22.2 % C, 1.72% N and a negligible amount of alumina. The resulting material had a BET surface area of 1095 m2/g, and an adsorption capacity for water and cyclohexane of l Og and more than 50 grams per 100 grams of sorbate, respectively.

In this example, the as-synthesized compound of Example 1 was functionalized with =
aluminum. A solution of 14.4 grams of ammonium acetate in 200 mi of ethanol was combined with 15 grams of aluminum di-isopropoxide acetoacetic ester chelate in 85 grams of ethanol.
10 grams of the as-synthesized MCM-41 compound prepared in Example 1 was slurried in the previously prepared solution of ammonium acetate and ester chelate. The resulting mixture was heated at 60 C overnight. A solid product was recovered by filtration and was air dried.
The yield of the solid product was 6.08 g. The product had the following percent composition: 75.4% ash (essentially all silica and alumina), 6.6% C, 0.64% N
and 13.6%
A1203. The composition of this product indicated that aluminum had been successfully inserted into the MCM-41 (36) porous matrix and the DTMA-Cl templating surfactant had been successfully removed. It was estimated that from at least 70% up to 99%
of the templating surfactant was removed in this experiment. The subsequently calcined product exhibited a BET surface area of 880 m2/g, and sorption for water and cyclohexane of 46.5g/100g and 36g/100g sorbate, respectively.

MCM-41 as synthesized in Example I was functionalized with tetraethyl ortho-silicate 1o (TEOS). A solution was prepared by combining 14.4 grams of ammonium acetate in 200 ml of ethanol with 10 grams of TEOS. The resulting solution was mixed with 10 grams of MCM-41 as synthesized in Example 1 to form a slurry. The resulting nzixture was heated overnight at 60 C. A solid product was recovered by filtration and air dried.
The yield of the solid product was 7.64g. The product had the following percent by weight composition:
86.1% ash, 5.73% C, 0.27% N. A subsequently calcined product exhibited a BET
surface area of 796 m2/g, and sorption for water of 32g/100g sorbate. The decreased BET value indicated that the pore volume of the as-synthesized MCM-41 had been reduced as a result of functionalizing with TEOS. Moreover, the decrease in carbon and nitrogen contents indicated that DTMA-Cl templating surfactant had been successfully removed. Based on the above present composition, it was estimated that from at least 85% to 99% of DTMA-Cl had been removed.

Siliceous MCM-4 1, a species of M41 S, was synthesized according to the procedure set forth below. 150 grams of Ultrasil precipated silica, 150 grams of 25% TMA-OH and 500 grams of water were reacted in a steambox for one hour. 400 grams of a 29%
solution of cetyltrimethylammonium chloride (CTMA-Cl) was added and the resulting mixture was reacted at 150 C for six hours.
The resulting product was recovered by filtration and dried in air at 110 C.
The X-ray diffraction pattern of the as-synthesized product exhibited a four-peak hexagonal pattern of MCM-41 with d-spacing of the first line at 45 A. The as-synthesized product had the following percent by weight composition: 35.8% ash, 24.5% carbon, 1.41%
nitrogen. After calcination, a 4-peak X-ray diffraction pattern indicative of MCM-41(40) was obtained. The resulting material had a BET surface area of 1069 m2/g and an adsorption capacity for water of 10 gams/100 grams sorbate.

MCM-41 as-synthesized in Example 4 was functionalized with Zr-hydroxychloride (ZrOC12). 10 grams of the compound prepared in Example 4 was slurried in a solution consisting of 20 grams of aqueous ZrOC12 solution (20% Zr02) and 60 ml of ethanol.

The resulting mixture was heated overnight at 60 C. A solid product was recovered by filtration and dried at 100 C. The solid product had a yield of 5.91g. The product contained 66.3% solids including 6.6% Zr. The zirconium functionalized MCM-41 product had a BET surface area of 938 m2/g. A decreased BET value and a high zirconium content 5 indicated that the ultra large pore material had been successfully fiunctionalized with zirconium. It is well known that in solution ZrOC12 forms cationic oxychloro clusters. The reduced ratio of % carbon/% solids after the treatment (0.5 after treatment vs. 0.8 before treatment) is indicative of considerable surfactant removal.

10 In this experiment cerium, a lanthanide, was inserted into an ultra large pore crystalline material. The cerium containing compound was also used to generate the cation donor neces-sary for displacement of the templating surfactant present in the as-synthesized MCM-4 1.
grams of as-synthesized MCM-41 prepared in Example 4 was slurried overnight at 60 in a solution containing 10 grams of cerium nitrate hexahydrate in 100 ml of ethanol. The 15 solid product was recovered by filtration and dried at 100 C. A yield of 11.43 grams was obtained. The functionalized product had the following composition by weight:
66% ash, 14.9% cerium, 16.6% carbon and 3.3 1% nitrogen. The BET surface area of the calcined functionalized product was 848 m2/g. The high concentration of cerium and decreased BET
value indicated that MCM-41 had been successfully functionalized with cerium.
Additionally, 20 a significantly decreased carbon content evidenced successful removal of CTMA-Cl, the templating surfactant utilized in the synthesis of MCM-4 1.

M41 S, synthesized as in Example 4 above, and containing 52.2% solids, 7.03%
alumina, 24.4% carbon, 2.07% nitrogen was treated in separate experiments with ethanol and water. In a first experiment, 10 grams of the as-synthesized M41 S was treated with a solution of 20 grams of cerium nitrate in 100 mL of ethanol and stirred overnight at room temperature.
In a second experiment, another 10 gram sample of the same M41 S was treated with a solution of 20 grams of cerium nitrate in 100 ml of water and stirred overnight at room temperature.
The product recovered affter filtration and drying from the first experiment contains 77% solids, 8.89% carbon and 2.19% nitrogen. The product recovered from the second experiment contains 63% solids, 19.6% carbon and 3.67% nitrogen. The percent surfactant retention is estimated by obtaining the ratio of percent carbon/percent solids. The surfactant rate of retention was 0.11 for the first experiment and 0.3 for the second experiment. These results indicate that by using an organic solvent such as ethanol it is possible to extract the templating surfactant at least 3 times more efficiently than if an aqueous solvent such as water were used.

In this example, a sample of ultra large pore crystalline material was functionalized with aluminum nitrate which was also used as a cation donor as required for the extraction of the templating surfactant from the as-synthesized zeolite.
20 grams of MCM-41 as prepared in Example 4 was slurried overnight at 60 C in a solution containing 10 grams of aluminum nitrate nonahydrate in 200 ml of ethanol. The solid product was recovered by filtration and dried at 100 C. The product had a yield of 10.4 grams and the following composition by weight percent: 74% ash, 4.7% alumina, 13.9%
carbon and 2.21% nitrogen. The calcined compound had a BET surface area of 934 m2/g.
1o When comparing the weight percent composition and BET values of the functionalized and as-synthesized MCM-41 compound, it is readily apparent that the functionalization with aluminum was successful. Similarly, a significant decrease in the carbon content indicated successful removal of CTMA, the templating surfactant used to prepare MCM-4 1.

This example demonstrates that if no exchanging moiety, such as a cation donor, is used in the extracting solvent, the efficiency of surfactant removal decreases dramatically.
M41 S was prepared by neutralizing a 400 grams water solution including 250 grams sodium silicate (28.8% silica, 8.8% Na20) with 125 grams water solution containing 16 grams of concentrated sulfuric acid. A 37% w/w DTMA-Cl solution in 425 grams of water was added to the previously prepared mixture. The resulting mixture was reacted at 100 C for 24 hours followed by another period of 24 hours at 150 C. The product recovered after filtration and drying showed a solid content, which was virtually all silica, of 27.3%
solids, 1.37%
nitrogen and 17% carbon. 15 grams of the foregoing solid was contacted with 200 ml of iso-propanol for 2 hours at 60 C. 7.06 grams of the resulting product was isolated and contained 54.1% solids, 2.18% nitrogen, 26.0% carbon. The % surfactant retention was estimated by taking the following formula:
R=(% N/% solids after treatment)/(%N/% solids before treatment) The percent surfactant retention for the previously prepared product was estimated to be 78%.
When the treatment was carried out by adding 20 grams of ammonium chloride salt as the cation doner to iso-propanol under milder conditions of room temperature, the product recovered (7.19 gram) contained 53.6% solids, 1.3 4% nitrogen and 16.3%
carbon. The surfactant retention factor was decreased to 49%. The latter surfactant retention value was further reduced to less that 20% by addition of water which caused complete solubilization of ammonium chloride in the exchanging solution.

Classifications
International ClassificationB01J29/03, B01J29/04, C01B37/02, B01J37/00, C01B39/04, C01B33/20, C01B33/12, B01J20/18
Cooperative ClassificationB01J29/0308, B01J2229/186, B01J2229/14, C01B37/02, B01J20/103, C01B39/026, B01J20/186, B01J29/041
European ClassificationB01J20/10B, B01J29/04A, B01J29/03A, B01J20/18D, C01B39/02P, C01B37/02
Legal Events
DateCodeEventDescription
31 Dec 2003EEERExamination request
17 Mar 2015MKLALapsed
Effective date: 20150203