# US 9,517,453 B2 · Methods for enhancing the mesoporosity of zeolite-containing materials > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,517,453 B2 - Document ID: US9517453B2 - Status: Granted - Kind: B2 - Application number: 14/229,878 - Filed: 2014-03-29 - Published: 2014-07-31 - Granted: 2016-12-13 - Earliest claimed: 2009-10-20 - Assignees: Rive Technology, Inc. - Applicants: Rive Technology, Inc. - Inventors: Javier Garcia Martinez; Lawrence B. Dight; Barry K. Speronello - Web page: https://patentgrep.com/patent/US9517453B2 ## CPC - B01J 29/084: {Y-type faujasite} - B01J 29/04: having base-exchange properties, e.g. crystalline zeolites {(B01J29/005 takes precedence)} - B01J 29/041: {Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41} - B01J 29/08: of the faujasite type, e.g. type X or Y - B01J 29/082: {X-type faujasite} - B01J 29/18: of the mordenite type - B01J 29/40: of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively - B01J 29/7015: {CHA-type, e.g. Chabazite, LZ-218} - B01J 35/60: characterised by their surface properties or porosity - B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} - B01J 35/635: {0.5-1.0 ml/g} - B01J 35/643: {less than 2 nm} - B01J 35/647: {2-50 nm} - B01J 35/69: bimodal - B01J 2229/22: to destroy the molecular sieve structure or part thereof - B01J 2229/37: Acid treatment - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS ## Abstract Methods for enhancing the mesoporosity of a zeolite-containing material. Such methods may comprise contacting a composite shaped article containing at least one zeolite and at least one non-zeolitic material with at least one pH controlling agent and at least one surfactant. Such methods may be performed under conditions sufficient to increase the pore volume of at least one 10 angstrom subset of mesoporosity. ## Claims ### Claim 1 A method of preparing a shaped zeolitic material with enhanced mesoporosity, said method comprising: (a) synthesizing a composite shaped article comprising at least one zeolite and at least one non-zeolitic material, wherein said zeolite comprises an aluminosilicate zeolite having a SiO2/Al2O3 ratio below about 20; and (b) contacting said composite shaped article with at least one pH controlling agent and at least one surfactant under conditions sufficient to increase the pore volume of at least one 10 angstrom subset of mesoporosity in said composite shaped article, thereby forming said shaped zeolitic material with enhanced mesoporosity, wherein said pH controlling agent comprises an acid or a base, wherein said contacting of step (b) causes a net mesopore increase in said zeolite of said composite shaped article. ### Claim 2 (depends on 1) The method of claim 1, wherein said contacting of step (b) causes a net increase of at least 10 percent in the overall mesoporosity of said composite shaped article, wherein said shaped zeolitic material has a total volume of mesopores in the range of from about 0.05 to about 0.9 cc/g. ### Claim 3 (depends on 1) The method of claim 1, wherein said increase in pore volume of said 10 angstrom subset constitutes an increase of at least 0.01 cc/g in said 10 angstrom subset. ### Claim 4 (depends on 1) The method of claim 1, wherein said increase in pore volume of said 10 angstrom subset constitutes an increase of at least 10 percent of the pore volume of said 10 angstrom subset. ### Claim 5 (depends on 1) The method of claim 1, wherein said 10 angstrom subset is contained within a range of 20 to 250 angstroms. ### Claim 6 (depends on 1) The method of claim 1, wherein step (a) includes the substeps of: (i) combining said at least one non-zeolitic material and said at least one zeolite to thereby form an initial mixture; and (ii) shaping said initial mixture into said composite shaped article. ### Claim 7 (depends on 1) The method of claim 1, wherein said at least one non-zeolitic material comprises aluminum oxide, titanium dioxide, zirconium oxide, mullite, hydrous kaolin clay, the residue of alkaline extraction of kaolin clay that has been calcined through the characteristic exotherm at about 1,780° F. without substantial formation of mullite, silicon carbide, silicon nitride, or mixtures thereof. ### Claim 8 (depends on 1) The method of claim 1, further comprising treating at least a portion of said shaped zeolitic material to extract at least a portion of aluminum therefrom. ### Claim 9 (depends on 1) The method of claim 1, wherein said zeolite comprises faujasite. ### Claim 10 (depends on 1) The method of claim 1, wherein said surfactant comprises a cationic surfactant. ### Claim 11 (depends on 1) The method of claim 1, wherein said surfactant comprises an alkylammonium halide. ### Claim 12 (depends on 1) The method of claim 1, wherein the reaction temperature of step (b) is in the range of from about 60 to about 100° C. ### Claim 13 (depends on 1) The method of claim 1, wherein said composite shaped article comprises said zeolite in an amount in the range of from about 0.1 to about 99 weight percent. ### Claim 14 (depends on 1) The method of claim 1, wherein said pH controlling agent comprises a base. ### Claim 15 A method of preparing a shaped zeolitic material with enhanced mesoporosity, said method comprising: (a) synthesizing a composite shaped article comprising at least one zeolite and at least one non-zeolitic material, wherein said zeolite comprises faujasite, mordenite, ZSM-5, CHA, or mixtures thereof; and (b) contacting said composite shaped article with an acid to form an acid-treated shaped article, wherein said contacting further comprises contacting said composite shaped article with at least one surfactant prior to, during, or after said contacting with said acid; and (c) contacting said acid-treated shaped article with a base to form a base-treated shaped article, wherein said base-treated shaped article has an overall mesoporosity that is at least 0.05 cc/g greater than said composite shaped article. ### Claim 16 (depends on 15) The method of claim 15, wherein said base-treated shaped article has an overall mesoporosity that is at least 0.1 cc/g greater than said composite shaped article, wherein said base-treated shaped article has a total volume of mesopores in the range of from about 0.05 to about 0.9 cc/g. ### Claim 17 (depends on 15) The method of claim 15, wherein said base-treated shaped article has an overall mesoporosity that is at least 50 percent greater than the overall mesoporosity of said composite shaped article. ### Claim 18 (depends on 15) The method of claim 15, wherein said base-treated shaped article comprises a mesostructured zeolite. ### Claim 19 (depends on 15) The method of claim 15, wherein said surfactant comprises an alkylammonium halide. ### Claim 20 A method of preparing a shaped zeolitic material with enhanced mesoporosity, said method comprising: (a) synthesizing a composite shaped article comprising at least one zeolite and at least one non-zeolitic material, wherein said zeolite comprises an aluminosilicate zeolite having a SiO2/Al2O3 ratio below about 20; (b) contacting said composite shaped article with an acid to form an acid-treated shaped article; (c) contacting said composite shaped article with at least one surfactant prior to, during, or after said contacting with said acid; and (d) contacting said acid-treated shaped article with a base to form a base-treated shaped article, wherein said base-treated shaped article has an overall mesoporosity that is greater than said composite shaped article. ### Claim 21 (depends on 20) The method of claim 20, wherein said base-treated shaped article has an overall mesoporosity that is at least 0.05 cc/g greater than said composite shaped article, wherein said base-treated shaped article has a total volume of mesopores in the range of from about 0.05 to about 0.9 cc/g. ### Claim 22 (depends on 20) The method of claim 20, wherein said base-treated shaped article has an overall mesoporosity that is at least 50 percent greater than the overall mesoporosity of said composite shaped article. ### Claim 23 (depends on 20) The method of claim 20, wherein said base-treated shaped article comprises a mesostructured zeolite. ### Claim 24 (depends on 20) The method of claim 20, wherein said surfactant comprises a cationic surfactant. ### Claim 25 (depends on 20) The method of claim 20, wherein said zeolite comprises faujasite, mordenite, ZSM-5, CHA, or mixtures thereof. ### Claim 26 (depends on 20) The method of claim 20, wherein said at least one non-zeolitic material comprises aluminum oxide, titanium dioxide, zirconium oxide, mullite, hydrous kaolin clay, the residue of alkaline extraction of kaolin clay that has been calcined through the characteristic exotherm at about 1,780° F. without substantial formation of mullite, silicon carbide, silicon nitride, or mixtures thereof. ### Claim 27 (depends on 20) The method of claim 20, wherein said composite shaped article comprises said zeolite in an amount in the range of from about 0.1 to about 99 weight percent.