# US 5,707,601 A · Process for preparing zeolites having MTT crystal structure using small, neutral amines > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,707,601 A - Document ID: US5707601A - Status: Granted - Kind: A - Application number: 08/610,537 - Filed: 1996-03-04 - Granted: 1998-01-13 - Earliest claimed: 1995-03-17 - Assignees: Chevron U.S.A. Inc. - Inventors: Yumi Nakagawa - Web page: https://patentgrep.com/patent/US5707601A ## CPC - C01B 39/48: using at least one organic template directing agent - Y10S 423/36: MTT, e.g. ZSM-23, ISI-1, KZ-1, EU-1, EU-4, EU-13 - C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract The present invention relates to a process for preparing zeolites having the MTT crystal structure, such as zeolites SSZ-32 and ZSM-23, using small, neutral amines capable of forming the zeolite, the amine containing (a) only carbon, nitrogen and hydrogen atoms, (b) one primary, secondary or tertiary, but not quaternary, amino group, and (c) a tertiary nitrogen atom, at least one tertiary carbon atom, or a nitrogen atom bonded directly to at least one secondary carbon atom (such as isobutylamine, diisobutylamine, diisopropylamine or trimethylamine), wherein the process is conducted in the absence of a quaternary ammonium compound. ## Claims ### Claim 1 A process for preparing a zeolite having, after calcination, the X-ray diffraction lines of Table I, said process comprising: (a) preparing an aqueous solution from (1) sources of an alkali metal oxide, alkaline earth metal oxide or mixtures thereof; (2) sources of an oxide selected from the oxides of aluminum, iron, gallium, indium, titanium, or mixtures thereof; (3) sources of an oxide selected from oxides of silicon, germanium or mixtures thereof; and (4) at least one small, neutral amine having a total of four to about eight carbon atoms and being capable of forming said zeolite, said amine containing (a) only carbon, nitrogen and hydrogen atoms, (b) one primary, secondary or tertiary, but not quaternary, amino group, and (c) a tertiary nitrogen atom, or at least one tertiary carbon atom, or a nitrogen atom bonded directly to at least one secondary carbon atom; (b) maintaining the aqueous solution under conditions sufficient to form crystals of the zeolite; and (c) recovering the crystals of the zeolite, wherein said process is conducted in the absence of a quaternary ammonium compound. ### Claim 2 (depends on 1) The process of claim 1 wherein said aqueous solution comprises, in terms of mole ratios, the following: ______________________________________ YO.sub.2 /W.sub.2 O.sub.3 .gtoreq.15 OH.sup.- /YO.sub.2 0.10-0.40 Q/YO.sub.2 0.05-0.50 M.sub.2/n /YO.sub.2 0.05-0.40 H.sub.2 O/YO.sub.2 10-70 ______________________________________ where Y is silicon, germanium or mixtures thereof; W is aluminum, iron, gallium, indium, titanium or mixtures thereof; Q is at least one small, neutral amine having a total of four to about eight carbon atoms and being capable of forming said zeolite, said amine containing (a) only carbon, nitrogen and hydrogen atoms, (b) one primary, secondary or tertiary, but not quaternary, amino group, and (c) a tertiary nitrogen atom, or at least one tertiary carbon atom, or a nitrogen atom bonded directly to at least one secondary carbon atom; M is an alkali metal, alkaline earth metal or mixtures thereof; and n is the valence of M. ### Claim 3 (depends on 2) The process of claim 2 wherein said aqueous solution comprises, in terms of mole ratios, the following: ______________________________________ YO.sub.2 /W.sub.2 O.sub.3 40 or more OH.sup.- /YO.sub.2 0.15-0.30 Q/YO.sub.2 0.10-0.30 M.sub.2/n /YO.sub.2 0.075-0.30 H.sub.2 O/YO.sub.2 .sub. 25-50.sub.-- ______________________________________ ### Claim 4 (depends on 2) The process of claim 2 wherein Y is silicon and W is aluminum. ### Claim 5 (depends on 4) The process of claim 4 wherein the YO.sub.2 /W.sub.2 O.sub.3 mole ratio is from about 20 to about 80. ### Claim 6 (depends on 4) The process of claim 4 wherein the YO.sub.2 /W.sub.2 O.sub.3 mole ratio is 40 or more. ### Claim 7 (depends on 4) The process of claim 4 wherein the YO.sub.2 /W.sub.2 O.sub.3 mole ratio is from about 40 to about 80. ### Claim 8 (depends on 1) The process of claim 1 wherein the small, neutral amine has the formula: (R.sup.1, R.sup.2, R.sup.3)N wherein the amine contains only carbon, hydrogen and nitrogen atoms; R.sup.1, R.sup.2, and R.sup.3 are H or C.sub.1 -C.sub.4 alkyl groups, provided that at least one of R.sup.1, R.sup.2 and R.sup.3 is alkyl; the amine contains a total of four to about eight carbon atoms; and the amine contains a tertiary nitrogen atom, or at least one tertiary carbon atom, or a nitrogen atom bonded directly to at least one secondary carbon atom. ### Claim 9 (depends on 1) The process of claim 1 wherein the small, neutral amine is selected from the group consisting of isobutylamine, diisobutylamine, and diisopropylamine. ### Claim 10 (depends on 4) The process of claim 4 wherein the amine is isobutylamine. ### Claim 11 (depends on 4) The process of claim 4 wherein the amine is diisobutylamine. ### Claim 12 (depends on 1) The process of claim 1 further comprising replacing the alkali metal cations, alkaline earth metal cations, or both of the recovered zeolite, at least in part, by ion exchange with a cation or mixture of cations selected from the group consisting of hydrogen and hydrogen precursors, rare earth metals, and metals from Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB, and VIII of the Periodic Table of Elements. ### Claim 13 (depends on 12) The process of claim 12 wherein said replacing cation is hydrogen or a hydrogen precursor. ### Claim 14 (depends on 1) The process of claim 1 wherein said process is performed in the absence of any nitrogen-containing organic templating agent other than the small, neutral amine. ### Claim 15 (depends on 1) The process of claim 1 wherein the crystallization in step (b) is substantially complete in 72 hours or less. ### Claim 16 A zeolite composition, as-synthesized and in the anhydrous state, having the X-ray diffraction lines of Table II and whose general formula, in terms of mole ratios, is as follows: ______________________________________ YO.sub.2 /W.sub.2 O.sub.3 .gtoreq.15 Q/YO.sub.2 0.02-0.10 M.sub.2/n /YO.sub.2 0.015-0.10 ______________________________________ wherein Y is silicon, germanium or a mixture thereof; W is aluminum, gallium, indium, iron, titanium, or mixtures thereof; Q is at least one small, neutral amine having a total of four to about eight carbon atoms and being capable of forming said zeolite, said amine containing (a) only carbon, nitrogen and hydrogen atoms, (b) one primary, secondary or tertiary, but not quaternary, amino group, and (c) a tertiary nitrogen atom, or at least one tertiary carbon atom, or a nitrogen atom bonded directly to at least one secondary carbon atom; M is an alkali metal cation, alkaline earth metal cation or mixtures thereof; and n is the valence of M, wherein said composition does not contain a quaternary ammonium compound. ### Claim 17 (depends on 16) The composition of claim 16 wherein Y is silicon and W is aluminum. ### Claim 18 (depends on 17) The composition of claim 17 wherein the YO.sub.2 /W.sub.2 O.sub.3 mole ratio is from about 20 to about 80. ### Claim 19 (depends on 17) The composition of claim 17 wherein the YO.sub.2 /W.sub.2 O.sub.3 mole ratio is 40 or more. ### Claim 20 (depends on 17) The composition of claim 17 wherein the YO.sub.2 /W.sub.2 O.sub.3 mole ratio is from about 40 to about 80. ### Claim 21 (depends on 16) The composition of claim 16 wherein the small, neutral amine has the formula: (R.sup.1, R.sup.2, R.sup.3)N wherein the amine contains only carbon, hydrogen and nitrogen atoms; R.sup.1, R.sup.2, and R.sup.3 are H or C.sub.1 -C.sub.4 alkyl groups, provided that at least one of R.sup.1, R.sup.2 and R.sup.3 is alkyl; the amine contains a total of four to about eight carbon atoms; and the amine contains a tertiary nitrogen atom, or at least one tertiary carbon atom, or a nitrogen atom bonded directly to at least one secondary carbon atom. ### Claim 22 (depends on 16) The composition of claim 16 wherein the small, neutral amine is selected from the group consisting of isobutylamine, diisobutylamine, and diisopropylamine. ### Claim 23 (depends on 17) The composition of claim 17 wherein the amine is isobutylamine. ### Claim 24 (depends on 17) The composition of claim 17 wherein the amine is diisobutylamine. ### Claim 25 (depends on 16) The composition of claim 16 wherein said composition does not contain any nitrogen-containing organic templating agent other than the small, neutral amine. ### Claim 26 A process for preparing a zeolite having, after calcination, the X-ray diffraction lines of Table I, said process comprising: (a) preparing an aqueous solution from (1) sources of an alkali metal oxide, alkaline earth metal oxide or mixtures thereof; (2) sources of an oxide selected from the oxides of aluminum, iron, gallium, indium, titanium, or mixtures thereof; (3) sources of an oxide selected from oxides of silicon, germanium or mixtures thereof; and (4) trimethylamine, diisobutylamine or diisopropylamine; (b) maintaining the aqueous solution under conditions sufficient to form crystals of the zeolite; and (c) recovering the crystals of the zeolite. ### Claim 27 (depends on 26) The process of claim 26 wherein said process is conducted in the absence of a quaternary ammonium compound. ### Claim 28 A zeolite composition, as-synthesized and in the anhydrous state, having the X-ray diffraction lines of Table II and whose general formula, in terms of mole ratios, is as follows: ______________________________________ YO.sub.2 /W.sub.2 O.sub.3 .gtoreq.15 Q/YO.sub.2 0.02-0.10 M.sub.2/n /YO.sub.2 0.015-0.10 ______________________________________ wherein Y is silicon, germanium or a mixture thereof; W is aluminum, gallium, indium, iron, titanium, or mixtures thereof; Q is trimethylamine, diisobutylamine or diisopropylamine; M is an alkali metal, alkaline earth metal or mixtures thereof; and n is the valence of M. ### Claim 29 (depends on 28) The composition of claim 28 wherein said composition does not contain a quaternary ammonium compound. ### Claim 30 A process for preparing a zeolite having, after calcination, the X-ray diffraction lines of Table I, said process comprising: (a) preparing an aqueous solution from (1) sources of an alkali metal oxide, alkaline earth metal oxide or mixtures thereof; (2) sources of an oxide selected from the oxides of aluminum, iron, gallium, indium, titanium, or mixtures thereof; (3) sources of an oxide selected from oxides of silicon, germanium or mixtures thereof; and (4) at least one small, neutral amine capable of forming said zeolite, said amine containing (a) only carbon, nitrogen and hydrogen atoms, (b) one primary, secondary or tertiary, but not quaternary, amino group, and (c) a tertiary nitrogen atom, or at least one tertiary carbon atom, or a nitrogen atom bonded directly to at least one secondary carbon atom; (b) maintaining the aqueous solution under conditions sufficient to form crystals of the zeolite; and (c) recovering the crystals of the zeolite, wherein said process is conducted in the absence of a quaternary ammonium compound, and wherein the mole ratio of (a)(3) to (a)(2) is from about 20 to less than 40. ### Claim 31 (depends on 30) The process of claim 30 wherein said aqueous solution comprises, in terms of mole ratios, the following: ______________________________________ YO.sub.2 /W.sub.2 O.sub.3 20-less than 40 OH.sup.- /YO.sub.2 0.10-0.40 Q/YO.sub.2 0.05-0.50 M.sub.2/n /YO.sub.2 0.05-0.40 H.sub.2 O/YO.sub.2 10-70 ______________________________________ where Y is silicon, germanium or mixtures thereof; W is aluminum, iron, gallium, indium, titanium or mixtures thereof; Q is at least one small, neutral amine capable of forming said zeolite, said amine containing (a) only carbon, nitrogen and hydrogen atoms, (b) one primary, secondary or tertiary, but not quaternary, amino group, and (c) a tertiary nitrogen atom, or at least one tertiary carbon atom, or a nitrogen atom bonded directly to at least one secondary carbon atom; M is an alkali metal, alkaline earth metal or mixtures thereof; and n is the valence of M. ### Claim 32 (depends on 31) The process of claim 31 wherein said aqueous solution comprises, in terms of mole ratios, the following: ______________________________________ YO.sub.2 /W.sub.2 O.sub.3 20-less than 40 OH.sup.- /YO.sub.2 0.15-0.30 Q/YO.sub.2 0.10-0.30 M.sub.2/n /YO.sub.2 0.075-0.30 H.sub.2 O/YO.sub.2 25-50. ______________________________________ ### Claim 33 (depends on 31) The process of claim 31 wherein Y is silicon and W is aluminum. ### Claim 34 (depends on 33) The process of claim 33 wherein the zeolite has, after calcination and in the hydrogen form, a Constraint Index of 13 or greater. ### Claim 35 (depends on 30) The process of claim 30 wherein the small, neutral amine has the formula: (R.sup.1, R.sup.2, R.sup.3)N wherein the amine contains only carbon, hydrogen and nitrogen atoms; R.sup.1, R.sup.2, and R.sup.3 are H or C.sub.1 -C.sub.4 alkyl groups, provided that at least one of R.sup.1, R.sup.2, and R.sup.3 is alkyl; the amine contains a total of about three to about eight carbon atoms; and the amine contains a tertiary nitrogen atom, or at least one tertiary carbon atom, or a nitrogen atom bonded directly to at least one secondary carbon atom. ### Claim 36 (depends on 30) The process of claim 30 wherein the small, neutral amine is selected from the group consisting of isobutylamine, diisobutylamine, diisopropylamine and trimethylamine. ### Claim 37 (depends on 33) The process of claim 33 wherein the amine is isobutylamine. ### Claim 38 (depends on 33) The process of claim 33 wherein the amine is diisobutylamine. ### Claim 39 (depends on 30) The process of claim 30 further comprising replacing the alkali metal cations, alkaline earth metal cations, or both of the recovered zeolite, at least in part, by ion exchange with a cation or mixture of cations selected from the group consisting of hydrogen and hydrogen precursors, rare earth metals, and metals from Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB, and VIII of the Periodic Table of Elements. ### Claim 40 (depends on 39) The process of claim 39 wherein said replacing cation is hydrogen or a hydrogen precursor. ### Claim 41 (depends on 30) The process of claim 30 wherein said process is performed in the absence of any nitrogen-containing organic templating agent other than the small, neutral amine. ### Claim 42 (depends on 30) The process of claim 30 wherein the crystallization in step (b) is substantially complete in 72 hours or less. ### Claim 43 A zeolite composition, as-synthesized and in the anhydrous state, having the X-ray diffraction lines of Table II and whose general formula, in terms of mole ratios, is as follows: ______________________________________ YO.sub.2 /W.sub.2 O.sub.3 20-less than 40 Q/YO.sub.2 0.02-0.10 M.sub.2/n /YO.sub.2 0.015-0.10 ______________________________________ wherein Y is silicon, germanium or a mixture thereof; W is aluminum, gallium, indium, iron, titanium, or mixtures thereof; Q is at least one small, neutral amine capable of forming said zeolite, said amine containing (a) only carbon, nitrogen and hydrogen atoms, (b) one primary, secondary or tertiary, but not quaternary, amino group, and (c) a tertiary nitrogen atom, or at least one tertiary carbon atom, or a nitrogen atom bonded directly to at least one secondary carbon atom; M is an alkali metal cation, alkaline earth metal cation or mixtures thereof; and n is the valence of M, wherein said composition does not contain a quaternary ammonium compound. ### Claim 44 (depends on 43) The composition of claim 43 wherein Y is silicon and W is aluminum. ### Claim 45 (depends on 44) The process of claim 44 wherein the zeolite has, after calcination and in the hydrogen form, a Constraint Index of 13 or greater. ### Claim 46 (depends on 43) The composition of claim 43 wherein the small, neutral amine has the formula: (R.sup.1, R.sup.2, R.sup.3)N wherein the amine contains only carbon, hydrogen and nitrogen atoms; R.sup.1, R.sup.2, and are H or C.sub.1 -C.sub.4 alkyl groups, provided that at least one of R.sup.1, R.sup.2, and R.sup.3 is alkyl; the amine contains a total of about three to about eight carbon atoms; and the amine contains a tertiary nitrogen atom, or at least one tertiary carbon atom, or a nitrogen atom bonded directly to at least one secondary carbon atom. ### Claim 47 (depends on 43) The composition of claim 43 wherein the small, neutral amine is selected from the group consisting of isobutylamine, diisobutylamine, diisopropylamine and trimethylamine. ### Claim 48 (depends on 44) The composition of claim 44 wherein the amine is isobutylamine. ### Claim 49 (depends on 44) The composition of claim 44 wherein the amine is diisobutylamine. ### Claim 50 (depends on 43) The composition of claim 43 wherein said composition does not contain any nitrogen-containing organic templating agent other than the small, neutral amine. ### Claim 51 A process for preparing a zeolite having, after calcination, the X-ray diffraction lines of Table I, said process comprising: (a) preparing an aqueous solution from (1) sources of an alkali metal oxide, alkaline earth metal oxide or mixtures thereof; (2) sources of an oxide selected from the oxides of aluminum, iron, gallium, indium, titanium, or mixtures thereof; (3) sources of an oxide selected from oxides of silicon, germanium or mixtures thereof; and (4) trimethylamine, diisobutylamine or diisopropylamine; (b) maintaining the aqueous solution under conditions sufficient to form crystals of the zeolite; and (c) recovering the crystals of the zeolite, wherein the mole ratio of (a)(3) to (a)(2) is from about 20 to less than 40. ### Claim 52 A zeolite composition, as-synthesized and in the anhydrous state, having the X-ray diffraction lines of Table II and whose general formula, in terms of mole ratios, is as follows: ______________________________________ YO.sub.2 /W.sub.2 O.sub.3 20-less than 40 Q/YO.sub.2 0.02-0.10 M.sub.2/n /YO.sub.2 0.015-0.10 ______________________________________ wherein Y is silicon, germanium or a mixture thereof; W is aluminum, gallium, indium, iron, titanium, or mixtures thereof; Q comprises trimethylamine, diisobutylamine or diisopropylamine; M is an alkali metal cation, alkaline earth metal cation or mixtures thereof; and n is the valence of M.