# US 10,766,781 B2 · Tin-containing zeolitic material having a BEA framework structure > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,766,781 B2 - Document ID: US10766781B2 - Status: Granted - Kind: B2 - Application number: 16/060,229 - Filed: 2016-12-07 - Published: 2018-12-20 - Granted: 2020-09-08 - Earliest claimed: 2015-12-08 - Assignees: BASF SE - Applicants: BASF SE - Inventors: Andrei-Nicolae Parvulescu; Joaquim Henrique Teles; Nicolas Vautravers; Ulrich Müller - Web page: https://patentgrep.com/patent/US10766781B2 ## CPC - C01B 39/08: the aluminium atoms being wholly replaced - B01J 29/035: {Microporous crystalline materials not having base exchange properties, such as} silica polymorphs, e.g. silicalites - B01J 29/7057: {Zeolite Beta} - B01J 29/86: Borosilicates; Aluminoborosilicates {(B01J29/005 takes precedence)} - B01J 35/615: {100-500 m2/g} - B01J 35/617: {500-1000 m2/g} - B01J 37/031: {Precipitation} - B01J 37/036: {to form a gel or a cogel} - B01J 37/10: in the presence of water, e.g. steam - C01B 37/02: Crystalline silica-polymorphs, e.g. silicalites {dealuminated aluminosilicate zeolites} - C01B 39/12: the replacing atoms being {at least} boron atoms - C01B 39/48: using at least one organic template directing agent - C07C 51/00: Preparation of carboxylic acids or their salts, halides or anhydrides (of acids by hydrolysis of oils, fats or waxes C11C) - C07C 51/02: from salts of carboxylic acids - C07C 67/00: Preparation of carboxylic acid esters - C07D 313/04: not condensed with other rings - C07F 5/02: Boron compounds - C07F 7/22: Tin compounds - B01J 2229/183: in framework positions - C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) - C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22) ## Abstract A process for preparing a tin-containing zeolitic material having framework type BEA, comprising providing an aqueous synthesis mixture comprising a boron source, a silicon source, and a BEA structure directing agent; subjecting the synthesis mixture provided in to hydrothermal pre-crystallization conditions; adding the tin source to the obtained mixture; subjecting the obtained aqueous synthesis mixture to hydrothermal crystallization conditions, obtaining a tin-containing zeolitic material having framework type BEA comprised in its mother liquor. ## Claims ### Claim 1 A tin-containing zeolitic material having framework type BEA, obtained by a process comprising (i.1) providing an aqueous synthesis mixture comprising a boron source, a silicon source, and a BEA structure directing agent; (i.2) subjecting the synthesis mixture provided in (i) to hydrothermal pre-crystallization conditions; (i.3) adding a tin source to the mixture obtained from (i.2); (i.4) subjecting the aqueous synthesis mixture obtained from (i.3) to hydrothermal crystallization conditions, obtaining a tin-containing zeolitic material having framework type BEA comprised in its mother liquor. ### Claim 2 (depends on 1) A process for preparing a tin-containing zeolitic material according to claim 1 having framework type BEA, comprising (i.1) providing an aqueous synthesis mixture comprising a boron source, a silicon source, and a BEA structure directing agent; (i.2) subjecting the synthesis mixture provided in (i) to hydrothermal pre-crystallization conditions; (i.3) adding the tin source to the mixture obtained from (i.2); (ii) subjecting the aqueous synthesis mixture obtained from (i.3) to hydrothermal crystallization conditions, obtaining a tin-containing zeolitic material having framework type BEA comprised in its mother liquor. ### Claim 3 (depends on 2) The process of claim 2, wherein at least 99 weight-% of the aqueous synthesis mixture provided in (i.1) consist of water, the boron source, the silicon source, and the framework type BEA structure directing agent, and wherein at least 99 weight-% of the aqueous synthesis mixture subjected to hydrothermal crystallization conditions in (ii) consist of the mixture obtained from (i.3) and the tin source. ### Claim 4 (depends on 2) The process of claim 2, wherein the hydrothermal pre-crystallization conditions according to (i.2) comprise a hydrothermal pre-crystallization temperature in the range of from 100 to 200° C. ### Claim 5 (depends on 2) The process of claim 2, wherein the tin source is one or more of tin(II) alkoxides, tin(IV) alkoxides, tin(II) salts of organic acids, tin(IV) salts of organic acids, tin(II) salts of inorganic acids, tin(IV) salts of inorganic acids; wherein the boron source is one or more of boric acid, borates, boron halides, and boron oxide (B2O3); wherein the silicon source is one or more of fumed silica and colloidal silica; and wherein the framework type BEA structure directing agent comprises tetraethylammonium hydroxide. ### Claim 6 (depends on 2) The process of claim 2, wherein in the aqueous synthesis mixture provided in (i.1), the weight ratio of boron relative to silicon is in the range of from 0.4:1 to 2.0:1; the weight ratio of the framework type BEA structure directing agent relative to silicon is in the range of from 0.10:1 to 0.30:1; and wherein in the aqueous synthesis mixture provided in (i.3), the weight ratio of tin relative to silicon is in the range of from 0.005:1 to 0.1:1. ### Claim 7 (depends on 2) The process of claim 2, wherein the hydrothermal crystallization conditions according to (ii) comprise a hydrothermal crystallization temperature in the range of from 100 to 200° C. ### Claim 8 (depends on 2) The process of claim 2, further comprising (iii) separating the tin-containing zeolitic material having framework type BEA from its mother liquor by washing the tin-containing zeolitic material having framework type BEA with a washing agent; (iv) subjecting the tin-containing zeolitic material having framework type BEA obtained from (iii) to drying conditions, at a drying temperature in the range of from 60 to 200° C.; (v) subjecting the tin-containing zeolitic material having framework type BEA obtained from (iv) to calcination conditions, at a calcination temperature in the range of from 400 to 700° C. ### Claim 9 (depends on 2) The process of claim 2, further comprising (vi) subjecting the tin-containing zeolitic material having framework type BEA to deboronation, obtaining a deboronated tin-containing zeolitic material, said subjecting to deboronation comprising (vi.1) treating the tin-containing zeolitic material having framework type BEA with an acid; (vi.2) washing the acid-treated tin-containing zeolitic material having framework type BEA with a washing agent, preferably water; or comprising (vi.1) treating the tin-containing zeolitic material having framework type BEA with water which does not contain an acid; (vi.2) optionally washing the water-treated tin-containing zeolitic material having framework type BEA with a washing agent, preferably water; wherein the treating according to (vi.1) is carried out at a temperature of the aqueous mixture comprising the tin-containing zeolitic material having framework type BEA, in the range of from 60 to 100° C. ### Claim 10 (depends on 9) The process of claim 9, further comprising (vii) subjecting the deboronated tin-containing zeolitic material having framework type BEA to drying conditions, at a drying temperature in the range of from 60 to 200° C.; (viii) subjecting the deboronated tin-containing zeolitic material having framework type BEA obtained from (vii) to calcination conditions, at a calcination temperature in the range of from 400 to 700° C. ### Claim 11 (depends on 2) The process of claim 2, wherein at least 99.5 weight-% of the aqueous synthesis mixture provided in (i.1) consist of water, the boron source, the silicon source, and the framework type BEA structure directing agent, and wherein at least 99.5 weight-%, of the aqueous synthesis mixture subjected to hydrothermal crystallization conditions in (ii) consist of the mixture obtained from (i.3) and the tin source. ### Claim 12 (depends on 2) The process of claim 2, wherein at least 99.9 weight-% of the aqueous synthesis mixture provided in (i.1) consist of water, the boron source, the silicon source, and the framework type BEA structure directing agent, and wherein at 99.9 weight-% of the aqueous synthesis mixture subjected to hydrothermal crystallization conditions in (ii) consist of the mixture obtained from (i.3) and the tin source. ### Claim 13 (depends on 2) The process of claim 2, wherein the hydrothermal pre-crystallization conditions according to (i.2) comprise a hydrothermal pre-crystallization temperature in the range of from 110 to 190° C. ### Claim 14 (depends on 2) The process of claim 2, wherein the hydrothermal pre-crystallization conditions according to (i.2) comprise a hydrothermal pre-crystallization temperature in the range of from 120 to 180° C. ### Claim 15 (depends on 2) The process of claim 2, wherein the tin source is Sn(II)-acetate or Sn(IV)-tert-butoxide; wherein the boron source is boric acid; wherein the silicon source ammonia-stabilized colloidal silica; and wherein the framework type BEA structure directing agent is tetraethylammonium hydroxide. ### Claim 16 A tin- and boron-containing zeolitic material having framework type BEA, having a tin content in the range of from 0.5 to 10 weight-%, calculated as elemental tin and based on the total weight of the tin- and boron-containing zeolitic material having framework type BEA, and having a boron content in the range of from 0. 5 to 9 weight-%, calculated as elemental boron and based on the total weight of the tin- and boron-containing zeolitic material having framework type BEA; and having an XRD spectrum comprising peaks at 2 theta diffraction angles of (8.0±0.1)° , (22.0±0.1)° , (23.0±0.1)° , (25.9±0.1)° , (27.3±0.1)° . ### Claim 17 (depends on 16) The tin- and boron-containing zeolitic material having framework type BEA of claim 16, further characterized by one or more of the following features: a BET specific surface of at least 400 m2/g, as determined according to DIN 66131; a crystallinity of at least 50%, as determined according to XRD; a micropore volume in the range of from 0.12 to 0.14 cm3/g, as determined according to DIN 66135; a mean crystal size of at most 100 nm, as determined according to SEM; an absorption band with a maximum in the range of from 200 to 220 nm and optionally a further absorption band with a maximum in the range of from 230 to 300 nm, as determined according to UV-VIS; an FT-IR spectrum wherein the ratio of the absorption maximum of a first band with a maximum in the range of from 3700 to 3750 cm−1 relative to the absorption maximum of a second band with a maximum in the range of from 3550 to 3699 cm−1 is in the range of from 0.5 to 2.0; a water uptake of at least 10 weight-%, as determined via water adsorption-desorption isotherms. ### Claim 18 A tin-containing zeolitic material having framework type BEA having a tin content in the range of from 0.5 to 10 weight %, calculated as elemental tin and based on the total weight of the tin-containing, zeolitic material having framework type BEA, and having a boron content in the range of from 0 to 0.15 weight-%, calculated as elemental boron and based on the total weight of the tin- and boron-containing zeolitic material having framework type BEA, wherein at least 99 weight-% of the zeolitic framework consist of Sn, B, Si, O, and H, having a crystallinity of at least 50%, as determined according to XRD, having a water uptake in the range of from 15 to 35 weight-%, as determined via water adsorption-desorption isotherms, and having an absorption band with a maximum in the range of from 200 to 220 nm and optionally a further absorption band with a maximum in the range of from 230 to 300 nm, as determined according to UV-VIS. ### Claim 19 (depends on 16) A catalytically active material comprising the tin- and boron-containing zeolitic material having framework type BEA according to claim 16. ### Claim 20 (depends on 18) A catalytically active material comprising the tin-containing zeolitic material having framework type BEA according to claim 18.