# US 5,707,600 A · Process for preparing medium pore size zeolites using neutral amines > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,707,600 A - Document ID: US5707600A - Status: Granted - Kind: A - Application number: 08/610,449 - Filed: 1996-03-04 - Granted: 1998-01-13 - Earliest claimed: 1995-03-17 - Assignees: Chevron U.S.A. Inc. - Inventors: Yumi Nakagawa; Stacey I. Zones - Web page: https://patentgrep.com/patent/US5707600A ## CPC - C01B 39/40: using at least one organic template directing agent - C01B 39/04: using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound - C01B 39/48: using at least one organic template directing agent - Y10S 423/22: MFI, e.g. ZSM-5. silicalite, LZ-241 - 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 medium pore size zeolites 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, wherein the process is conducted in the absence of a quaternary ammonium compound. ## Claims ### Claim 1 A process for preparing a unidimensional, medium pore size zeolite which comprises: (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 the zeolite, said amine containing four to about eight carbon atoms and (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 15-100 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 the zeolite, said amine containing four to about eight carbon atoms and (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, wherein said process is conducted in the absence of a quaternary ammonium compound. ### 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 25-50 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 4 (depends on 1) The process of claim 1 wherein the small, neutral amine is selected from the group consisting of isobutylamine, diisobutylamine, diisopropylamine, sec-butylamine, 2,5-dimethylpyrrolidine and 2,6-dimethylpiperidine. ### Claim 5 (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 6 (depends on 5) The process of claim 5 wherein said replacing cation is hydrogen or a hydrogen precursor. ### Claim 7 (depends on 1) The process of claim 1 wherein the medium pore size zeolite is theta-1. ### Claim 8 (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 9 A unidimensional, medium pore size zeolite composition, as-synthesized and in the anhydrous state, 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 capable of forming the zeolite, said amine containing four to about eight carbon atoms and (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 alkali metal cation, alkaline earth metal cations or mixtures thereof, n is the valence of M, wherein said composition does not contain a quaternary ammonium compound. ### Claim 10 (depends on 9) The medium pore size zeolite composition of claim 9 wherein the small, neutral amine is selected from the group consisting of isobutylamine, diisobutylamine, diisopropylamine, sec-butylamine, 2,5-dimethylpyrrolidine and 2,6-dimethylpiperidine. ### Claim 11 (depends on 10) The medium pore size zeolite composition of claim 10 having the X-ray diffraction lines of Table III. ### Claim 12 (depends on 10) The medium pore size zeolite composition of claim 10 wherein said composition does not contain any nitrogen-containing organic templating agent other than the small, neutral amine. ### Claim 13 A process for preparing the zeolite ZSM-5 having the X-ray diffraction lines of Table II which comprises: (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) cyclopentylamine; (b) maintaining the aqueous solution under conditions sufficient to form crystals of the zeolite; and (c) recovering the crystals of the zeolite. ### Claim 14 (depends on 13) The process of claim 13 wherein said aqueous solution comprises, in terms of mole ratios, the following: ______________________________________ YO.sub.2 /W.sub.2 O.sub.3 15-100 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 cyclopentylamine; M is an alkali metal, alkaline earth metal or mixtures thereof; and n is the valence of M. ### Claim 15 (depends on 13) The process of claim 13 wherein said process is conducted in the absence of a quaternary ammonium compound. ### Claim 16 (depends on 13) The process of claim 13 wherein said process is conducted in the absence of any nitrogen-containing organic templating agent other than the cyclopentylamine. ### Claim 17 The zeolite ZSM-5, as-synthesized and in the anhydrous state, 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 cyclopentylamine; M is alkali metal cation, alkaline earth metal cations or mixtures thereof, and n is the valence of M. ### Claim 18 (depends on 17) The zeolite of claim 17 wherein said zeolite does not contain a quaternary ammonium compound. ### Claim 19 (depends on 17) The zeolite of claim 17 wherein said zeolite does not contain any nitrogen-containing organic templating agent other than the cyclopentylamine.