# US 9,580,329 B2 · Introduction of mesoporosity into low silica zeolites > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,580,329 B2 - Document ID: US9580329B2 - Status: Granted - Kind: B2 - Application number: 13/740,839 - Filed: 2013-01-14 - Published: 2013-07-18 - Granted: 2017-02-28 - Earliest claimed: 2012-01-13 - Assignees: Rive Technology, Inc. - Applicants: Rive Technology, Inc. - Inventors: Kunhao Li; Javier Garcia-Martinez; Michael G. Beaver - Web page: https://patentgrep.com/patent/US9580329B2 ## CPC - C01B 39/026: {After-treatment} - B01J 29/041: {Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41} - B01J 29/082: {X-type faujasite} - B01J 29/7003: {A-type} - C01B 39/04: using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound - C01B 39/14: Type A - C01B 39/22: Type X {(C01B39/205 takes precedence)} - B01J 35/63: Pore volume - B01J 35/633: {less than 0.5 ml/g} - B01J 35/647: {2-50 nm} - B01J 35/69: bimodal - B01J 37/0018: {Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)} - 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 ## Abstract Mesoporous X and A zeolites and methods for production thereof are disclosed herein. Such mesoporous zeolites can be prepared by contacting an initial zeolite with an acid in conjunction with a mesopore forming agent. The initial zeolite can have a framework silicon-to-aluminum content in the range of from about 1 to about 2.5. Additionally, such mesoporous zeolites can have a total 20 to 135 Å diameter mesopore volume of at least 0.05 cc/g. ## Claims ### Claim 1 A method of forming a material comprising a mesoporous zeolite, said method comprising: (a) contacting an initial large pore zeolite with a mesopore forming agent to thereby form a first treatment mixture comprising an agent-treated zeolite and said mesopore forming agent; (b) contacting said first treatment mixture with an acid to thereby form a second treatment mixture comprising an acid-treated zeolite, said acid, and said mesopore forming agent; and (c) contacting said acid-treated zeolite with a base to thereby form a base-treated zeolite having a greater 20 to 135 Å diameter mesopore volume than said initial zeolite, wherein said initial large pore zeolite has a framework silicon-to-aluminum ratio (“Si/Al”) of less than 2.5. ### Claim 2 (depends on 1) The method of claim 1, wherein said base-treated zeolite has a total 20 to 135 Å diameter mesopore volume of at least 0.05 cc/g. ### Claim 3 (depends on 1) The method of claim 1, wherein said base-treated zeolite has a crystalline content of at least 10 weight percent as measured by X-ray diffraction (“XRD”). ### Claim 4 (depends on 1) The method of claim 1, wherein said base-treated zeolite has a total 20 to 135 Å diameter mesopore volume that is at least 0.02 cc/g greater than the 20 to 135 Å diameter mesopore volume of said initial large pore zeolite. ### Claim 5 (depends on 1) The method of claim 1, wherein said initial large pore zeolite is selected from the group consisting of zeolite A and zeolite X. ### Claim 6 (depends on 1) The method of claim 1, wherein said base-treated zeolite is a mesostructured zeolite. ### Claim 7 (depends on 1) The method of claim 1, wherein said acid is present in an initial amount in the range of from about 1 to about 10 milliequivalents per gram of said initial large pore zeolite. ### Claim 8 (depends on 1) The method of claim 1, wherein said acid is present in an initial amount in the range of from about 2 to about 6 milliequivalents per gram of said initial large pore zeolite. ### Claim 9 (depends on 1) The method of claim 1, wherein said mesopore forming agent comprises a surfactant selected from the group consisting of cetyltrimethylammomium bromide, cetyltrimethylammonium chloride, and mixtures thereof. ### Claim 10 (depends on 1) The method of claim 1, wherein said base is present in a ratio with the initial quantity of said initial large pore zeolite in the range of from about 0.1 to 20 mmol per gram of initial zeolite. ### Claim 11 (depends on 1) The method of claim 1, wherein said base is selected from the group consisting of NaOH, NH4OH, KOH, Na2CO3, TMAOH, and mixtures thereof. ### Claim 12 (depends on 1) The method of claim 1, wherein said acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, sulfonic acid, oxalic acid, citric acid, ethylenediaminetetraacetic acid, tartaric acid, malic acid, glutaric acid, succinic acid, and mixtures of two or more thereof. ### Claim 13 A method of forming a material comprising a mesoporous zeolite, said method comprising: (a) contacting an initial large pore zeolite having a framework silicon-to-aluminum ratio in the range of from about 1 to about 2.5 with a mesopore forming agent to thereby produce a first treatment mixture comprising an initially-treated zeolite and said mesopore forming agent; (b) introducing an acid into said first treatment mixture to thereby form a second treatment mixture comprising an acid-treated zeolite, said mesopore forming agent, and said acid; and (c) contacting said acid-treated zeolite with a base to thereby form a base-treated zeolite having a greater 20 to 135 Å diameter mesopore volume than said initial large pore zeolite, wherein said base-treated zeolite has a total 20 to 135 Å diameter mesopore volume of at least 0.05 cc/g. ### Claim 14 (depends on 13) The method of claim 13, wherein said base-treated zeolite has a total 20 to 135 Å diameter mesopore volume of at least 0.1 cc/g. ### Claim 15 (depends on 13) The method of claim 13, wherein said base-treated zeolite has a crystalline content of at least 10 weight percent as measured by X-ray diffraction (“XRD”). ### Claim 16 (depends on 13) The method of claim 13, wherein said base-treated zeolite has a total 20 to 135 Å diameter mesopore volume that is at least 0.02 cc/g greater than the 20 to 135 Å diameter mesopore volume of said initial large pore zeolite. ### Claim 17 (depends on 13) The method of claim 13, wherein said initial large pore zeolite is selected from the group consisting of zeolite A and zeolite X. ### Claim 18 (depends on 13) The method of claim 13, wherein said initial large pore zeolite is a zeolite A. ### Claim 19 (depends on 13) The method of claim 13, wherein said base-treated zeolite is a mesostructured zeolite. ### Claim 20 (depends on 13) The method of claim 13, wherein said acid is present in an initial amount in the range of from about 1 to about 10 milliequivalents per gram of said initial large pore zeolite. ### Claim 21 (depends on 13) The method of claim 13, wherein said acid is present in an initial amount in the range of from about 2 to about 6 milliequivalents per gram of said initial large pore zeolite. ### Claim 22 (depends on 13) The method of claim 13, wherein said acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, sulfonic acid, oxalic acid, citric acid, ethylenediaminetetraacetic acid, tartaric acid, malic acid, glutaric acid, succinic acid, and mixtures of two or more thereof. ### Claim 23 (depends on 13) The method of claim 13, wherein said surfactant is selected from the group consisting of cetyltrimethylammomium bromide, cetyltrimethylammonium chloride, and mixtures thereof. ### Claim 24 (depends on 13) The method of claim 13, wherein said base is selected from the group consisting of NaOH, NH4OH, KOH, Na2CO3, TMAOH, and mixtures thereof.