# US 10,864,500 B2 · High geometric surface area catalysts for vinyl acetate monomer production > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,864,500 B2 - Document ID: US10864500B2 - Status: Granted - Kind: B2 - Application number: 16/708,966 - Filed: 2019-12-10 - Published: 2020-04-09 - Granted: 2020-12-15 - Earliest claimed: 2015-07-22 - Assignees: BASF SE - Applicants: BASF Corporation - Inventors: Dieter G. Von Deak - Web page: https://patentgrep.com/patent/US10864500B2 ## CPC - B01J 23/52: Gold - B01J 31/02: containing organic compounds or metal hydrides - B01J 31/0205: {comprising carbonyl groups or oxygen-containing derivatives, e.g. acetals, ketals, cyclic peroxides} - B01J 31/04: containing carboxylic acids or their salts {(B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226)} - B01J 35/32: Bulk density - B01J 35/40: characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77) - B01J 35/50: characterised by their shape or configuration - B01J 35/615: {100-500 m2/g} - B01J 35/617: {500-1000 m2/g} - B01J 35/618: {more than 1000 m2/g} - B01J 37/02: Impregnation, coating or precipitation ({B01J37/0009 and B01J37/0018 take precedence } ; protection by coating B01J33/00) - B01J 37/0201: {Impregnation} - B01J 37/024: {Multiple impregnation or coating} - B01J 37/16: Reducing - C07C 67/055: in the presence of platinum group metals or their compounds - B01J 21/12: Silica and alumina - B01J 23/44: Palladium - B01J 31/0274: {containing silicon (ligands in coordination complexes B01J31/1608)} - B01J 2235/00: Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties - B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract A catalyst includes a support, where the support includes an external surface, about 60 wt % to about 99 wt % silica, and about 1.0 wt % to about 5.0 wt % alumina. A catalytic layer is disposed within the support adjacent to the external surface, where the catalytic layer further includes Pd, Au, and potassium acetate (KOAc). In the catalyst, (a) the KOAc is from about 60 kg/m3 to about 150 kg/m3 of the catalyst; or (b) the catalytic layer has an average thickness from about 50 μm to about 150 μm; or (c) both (a) and (b). The catalyst also possesses a Brunauer-Emmett-Teller surface area of about 130 m2/g to about 300 m2/g and a geometric surface area per packed bed volume from about 550 m2/m3 to about 1500 m2/m3. The catalyst is highly active for the synthesis of vinyl acetate monomer and exhibits a high selectivity for vinyl acetate monomer. ## Claims ### Claim 1 A catalyst comprising: a support comprising: an external surface; about 60 wt % to about 99 wt % silica; and about 1.0 wt % to about 5.0 wt % alumina; a catalytic layer disposed within the support adjacent to the external surface, where the catalytic layer further comprises Pd, Au, and potassium acetate (KOAc); a Brunauer-Emmett-Teller surface area of about 130 m2/g to about 300 m2/g; and a geometric surface area per packed bed volume from about 550 m2/m3 to about 1500 m2/m3; wherein the void fraction of the catalyst is from about 35% to about 55%; and wherein; (a) the KOAc is from about 60 kg/m3 to about 150 kg/m3 of the catalyst; (b) the catalytic layer has an average thickness from about 50 μm to about 150 μm, or (c) the KOAc is from about 60 kg/m3 to about 150 kg/m3 of the catalyst and the catalytic layer has an average thickness from about 50 μm to about 150 μm. ### Claim 2 (depends on 1) The catalyst of claim 1, wherein the KOAc is from about 65 kg/m3 to about 100 kg/m3 of the catalyst. ### Claim 3 (depends on 1) The catalyst of claim 1, wherein the alumina is present in the catalyst from about 1.0 wt % to about 3.0 wt %, Pd is present in the catalyst is from about 3 g/L to about 15 g/L, and the Au is present in the catalyst is from about 0.9 g/L to about 7.0 g/L. ### Claim 4 (depends on 1) The catalyst of claim 1, wherein the mass ratio of Pd to Au is from about 3.5:1 to about 2.0:1. ### Claim 5 (depends on 1) The catalyst of claim 1, wherein the Brunauer-Emmett-Teller surface area of the catalyst is from about 200 m2/g to about 250 m2/g. ### Claim 6 (depends on 1) The catalyst of claim 1, wherein the geometric surface area per packed bed volume of the catalyst is from about 600 m2/m3 to about 1500 m2/m3. ### Claim 7 (depends on 1) The catalyst of claim 1, wherein the geometric surface area per packed bed volume of the catalyst is from about 800 m2/m3 to about 1300 m2/m3. ### Claim 8 (depends on 1) The catalyst of claim 1, wherein with the exception of the catalytic layer, the support is substantially free of Pd, Au, and KOAc. ### Claim 9 (depends on 1) The catalyst of claim 1, wherein the KOAc is from about 65 kg/m3 to about 100 kg/m3 of the catalyst and the catalytic layer has an average thickness from about 50 μm to about 150 μm. ### Claim 10 (depends on 9) The catalyst of claim 9, wherein the catalyst is in a shape selected from the group consisting of cylindrical, spherical, tubular, polylobular, ring, star, saddle, fluted, ridged, or mixture of any two or more thereof. ### Claim 11 (depends on 1) The catalyst of claim 1, wherein the KOAc is from about 65 kg/m3 to about 100 kg/m3 of the catalyst; the catalytic layer has an average thickness from about 50 μm to about 150 μm; and the geometric surface area per packed bed volume of the catalyst is from about 600 m2/m3 to about 1500 m2/m3. ### Claim 12 A method of making a catalyst comprising: a support material comprising: an external surface; about 60 wt % to about 99 wt % silica; and about 1.0 wt % to about 5.0 wt % alumina; a catalytic layer disposed within the support adjacent to the external surface, where the catalytic layer further comprises Pd, Au, and potassium acetate (KOAc); a Brunauer-Emmett-Teller surface area of about 130 m2/g to about 300 m2/g; and a geometric surface area per packed bed volume from about 550 m2/m3 to about 1500 m2/m3; wherein the void fraction of the catalyst is from about 35% to about 55%; and wherein; (a) the KOAc is from about 60 kg/m3 to about 150 kg/m3 of the catalyst; (b) the catalytic layer has an average thickness from about 50 μm to about 150 μm, or (c) the KOAc is from about 60 kg/m3 to about 150 kg/m3 of the catalyst and the catalytic layer has an average thickness from about 50 μm to about 150 μm; the method comprising permeating the support material with Pd, Au, and KOAc to provide the catalytic layer disposed within the support material adjacent to the external surface. ### Claim 13 (depends on 12) The method of claim 12, wherein permeating the support material comprises contacting the support material with a salt solution comprising a salt of Pd, a salt of Au, or a mixture thereof. ### Claim 14 (depends on 13) The method of claim 13, wherein subsequent to contacting with the salt solution, permeating the support material comprises contacting the support material with a basic solution. ### Claim 15 (depends on 13) The method of claim 13, further comprising a washing step subsequent to the permeating step. ### Claim 16 (depends on 12) The method of claim 12, further comprising exposing the catalytic layer to a reducing agent. ### Claim 17 (depends on 16) The method of claim 16, wherein the exposing step occurs at a temperature from about 15° C. to about 500° C. ### Claim 18 A process for producing vinyl acetate monomer comprising contacting a reactant gas with a catalyst to produce the vinyl acetate monomer; wherein the reactant gas comprises ethylene, acetic acid, and O2; and wherein the catalyst comprises: a support comprising: an external surface; about 60 wt % to about 99 wt % silica; and about 1.0 wt % to about 5.0 wt % alumina; a catalytic layer disposed within the support adjacent to the external surface, where the catalytic layer further comprises Pd, Au, and potassium acetate (KOAc); a Brunauer-Emmett-Teller surface area of about 130 m2/g to about 300 m2/g; and a geometric surface area per packed bed volume from about 550 m2/m3 to about 1500 m2/m3; wherein the void fraction of the catalyst is from about 35% to about 55%; and wherein: (a) the KOAc is from about 60 kg/m3 to about 150 kg/m3 of the catalyst; (b) the catalytic layer has an average thickness from about 50 μm to about 150 μm, or (c) the KOAc is from about 60 kg/m3 to about 150 kg/m3 of the catalyst and the catalytic layer has an average thickness from about 50 μm to about 150 μm.