# US 9,040,443 B2 · Catalysts for making ethanol from acetic acid > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,040,443 B2 - Document ID: US9040443B2 - Status: Granted - Kind: B2 - Application number: 13/916,000 - Filed: 2013-06-12 - Published: 2013-11-07 - Granted: 2015-05-26 - Earliest claimed: 2008-07-31 - Assignees: Celanese International Corporation - Applicants: Celanese International Corporation - Inventors: Victor J. Johnston; Barbara F. Kimmich; John L. Potts; Heiko Weiner; Radmila Wollrab; James H. Zink; Josefina T. Chapman; Laiyuan Chen - Web page: https://patentgrep.com/patent/US9040443B2 ## CPC - B01J 23/6567: {Rhenium} - B01J 23/002: {Mixed oxides other than spinels, e.g. perovskite} - B01J 23/26: Chromium - B01J 23/40: of the platinum group metals - B01J 23/58: with alkali- or alkaline earth metals - B01J 23/60: with zinc, cadmium or mercury - B01J 23/626: {with tin} - B01J 23/70: of the iron group metals or copper - B01J 37/0205: {in several steps} - B01J 37/0207: {Pretreatment of the support} - C07C 29/149: with hydrogen or hydrogen-containing gases - C07C 67/00: Preparation of carboxylic acid esters - B01J 21/16: Clays or other mineral silicates - 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 Catalysts and processes for forming catalysts for use in hydrogenating acetic acid to form ethanol. In one embodiment, the catalyst comprises a first metal, a silicaceous support, and at least one metasilicate support modifier. Preferably, the first metal is selected from the group consisting of copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum, and tungsten. In addition the catalyst may comprise a second metal preferably selected from the group consisting of copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold, and nickel. ## Claims ### Claim 1 A process for preparing a catalyst, the process comprising the steps of: (a) contacting a first metal precursor to a first metal with a modified silicaceous support to form an impregnated support, wherein the modified silicaceous support comprises a silicaceous material and at least one metasilicate support modifier; and (b) heating the impregnated support under conditions effective to reduce the first metal and form the catalyst. ### Claim 2 (depends on 1) The process of claim 1, further comprising the steps of: (c) contacting the at least one metasilicate support modifier or a precursor thereof with the silicaceous material to form a modified support precursor; (d) heating the modified support precursor under conditions effective to form the modified support. ### Claim 3 (depends on 1) The process of claim 1, wherein at least part of the heating occurs under a reducing atmosphere. ### Claim 4 (depends on 1) The process of claim 1, further comprising the step of calcining the catalyst. ### Claim 5 (depends on 1) The process of claim 1, wherein the at least one metasilicate support modifier is selected from the group consisting of (i) alkaline earth metal metasilicates, (ii) alkali metal metasilicates, (iii) Group IIB metal metasilicates, (iv) Group IIIB metal metasilicates, and mixtures thereof. ### Claim 6 (depends on 1) The process of claim 1, wherein the first metal is selected from the group consisting of copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum, and tungsten. ### Claim 7 (depends on 1) The process of claim 1, wherein the first metal is present in an amount of from 0.1 to 25 wt. %, based on the total weight of the catalyst. ### Claim 8 (depends on 1) The process of claim 1, wherein the at least one metasilicate support modifier is selected from metasilicates of a metal selected from the group consisting of sodium, potassium, magnesium, scandium, yttrium, calcium and zinc. ### Claim 9 (depends on 1) The process of claim 1, wherein the at least one metasilicate support modifier is present in the catalyst in an amount of 0.1 wt. % to 50 wt. %, based on the total weight of the catalyst. ### Claim 10 (depends on 1) The process of claim 1, wherein the modified silicaceous support is present in the catalyst in an amount from 25 wt. % to 99 wt. %, based on the total weight of the catalyst. ### Claim 11 (depends on 1) The process of claim 1, wherein the silicaceous material is selected from the group consisting of silica, silica/alumina, calcium metasilicate, pyrogenic silica, high purity silica and mixtures thereof. ### Claim 12 (depends on 1) The process of claim 1, further comprising the steps of impregnating and reducing a second metal precursor to a second metal different from the first metal on the support either before, after, or concurrently with steps (a) and (b). ### Claim 13 (depends on 12) The process of claim 12, wherein the first metal is platinum and the second metal is tin. ### Claim 14 (depends on 13) The process of claim 13, wherein the molar ratio of platinum to tin in the catalyst is from 0.4:0.6 to 0.6:0.4. ### Claim 15 (depends on 12) The process of claim 12, wherein the first metal is palladium and the second metal is rhenium. ### Claim 16 (depends on 15) The process of claim 15, wherein the molar ratio of rhenium to palladium in the catalyst is from 0.7:0.3 to 0.85:0.15. ### Claim 17 (depends on 12) The process of claim 12, wherein the second metal is selected from the group consisting of copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold, and nickel; and wherein the second metal is present in the catalyst in an amount of from 0.1 to 10 wt. %, based on the total weight of the catalyst. ### Claim 18 (depends on 12) The process of claim 12, further comprising the steps of impregnating and reducing a third metal precursor to a third metal different from the first metal and the second metal on the support either before, after, or concurrently with steps (a) and (b). ### Claim 19 (depends on 18) The process of claim 18, wherein the third metal is selected from the group consisting of cobalt, palladium, ruthenium, copper, zinc, platinum, tin, and rhenium and wherein the third metal is present in the catalyst in an amount from 0.05 to 4 wt. %, based on the total weight of the catalyst. ### Claim 20 A process for preparing a catalyst, the process comprising the steps of: (a) providing a modified silicaceous support comprising a silicaceous material and at least one metasilicate support modifier selected from metasilicates of a metal selected from the group consisting of sodium, potassium, magnesium, scandium, yttrium, and zinc; (b) simultaneously contacting a first metal precursor to a first metal and a second metal precursor to a second metal with the modified silicaceous support to form an impregnated support, wherein the first metal is selected from the group consisting of copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum, and tungsten, and the second metal, being different than the first metal, is selected from the group consisting of copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold, and nickel; and (c) heating the impregnated support under conditions effective to reduce the first metal and form the catalyst.