# US 8,785,697 B2 · Nickel modified catalyst for the production of hydroxy ether hydrocarbons by vapor phase hydrogenolysis of cyclic acetals and ketals > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,785,697 B2 - Document ID: US8785697B2 - Status: Granted - Kind: B2 - Application number: 13/168,361 - Filed: 2011-06-24 - Published: 2012-12-27 - Granted: 2014-07-22 - Earliest claimed: 2011-06-24 - Assignees: Eastman Chemical Company - Applicants: Damon Ray Billodeaux; Thomas James Devon; Brent Alan Tennant; Charles Edwan Sumner, Jr. - Inventors: Damon Ray Billodeaux; Thomas James Devon; Brent Alan Tennant; Charles Edwan Sumner, Jr. - Web page: https://patentgrep.com/patent/US8785697B2 ## CPC - C07C 41/28: from acetals, e.g. by dealcoholysis - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract Catalyst compositions of alumina supports containing palladium and nickel are selective in a vapor phase hydrogenolysis reaction to convert cyclic acetal compounds and/or cyclic ketal compounds in the presence of hydrogen to their corresponding hydroxy ether hydrocarbon reaction products. ## Claims ### Claim 1 A hydrogenolysis process comprising contacting hydrogen with a cyclic compound composition comprising cyclic acetal compounds, cyclic ketal compounds, or a combination thereof in the vapor phase and in the presence of a catalyst composition to produce a hydroxy ether hydrocarbon composition, wherein the catalyst composition comprises an aluminum oxide support containing or on which is deposited: i. palladium present in an amount of at least 0.8 wt % and up to 5 wt % based on the weight of the catalyst composition, and ii. nickel present in an amount of 100 ppmw up to 5000 ppmw based on the weight of the catalyst composition. ### Claim 2 (depends on 1) The process of claim 1, wherein the BET surface area of the alumina is within a range from 10 m2/g to 300 m2/g. ### Claim 3 (depends on 1) The process of claim 1, wherein the alumina support is an α-alumina support having an alpha phase content of at least 95%. ### Claim 4 (depends on 1) The process of claim 1, wherein palladium is present in an amount of at least 0.9 wt % and up to 2 wt %. ### Claim 5 (depends on 1) The process of claim 1, wherein silicon dioxide, if present in the catalyst composition, does not exceed 0.2 wt %. ### Claim 6 (depends on 1) The process of claim 1, wherein the amount of nickel does not exceed 2000 ppmw. ### Claim 7 (depends on 1) The process of claim 1, wherein the catalyst composition comprises palladium in an amount of up to 2 wt %, silicon dioxide, if present, in an amount not exceeding 0.2 wt %, and nickel present in an amount not exceeding 2000 ppm. ### Claim 8 (depends on 1) The process of claim 1, wherein the catalyst composition is free of alkali metal in an amount exceeding 30 ppmw. ### Claim 9 (depends on 1) The process of claim 1, wherein the conversion of cyclic compound is at least 70% and the selectivity to the production of hydroxy ether monohydrocarbons is at least 85%. ### Claim 10 (depends on 9) The process of claim 9, wherein the selectivity is at least 90%. ### Claim 11 (depends on 10) The process of claim 10, wherein the conversion is at least 75%. ### Claim 12 (depends on 11) The process of claim 11, wherein the cyclic compound comprises a cyclic acetal. ### Claim 13 (depends on 12) The process of claim 12, wherein a diether co-product is generated in an amount of less than 5 wt %. ### Claim 14 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13) The process of any one of claims 1-13, comprising: (a) feeding hydrogen and the cyclic compound composition to a reaction zone within a reaction vessel, and (b) conducting a reaction in the reaction zone comprising contacting hydrogen with at least a portion of the cyclic compound composition in the reaction zone under reaction zone conditions above the dew point of the cyclic compound composition to produce hydroxy ether hydrocarbons, fed to the reaction zone, and (c) withdrawing a product stream from the reaction zone comprising hydroxy ether hydrocarbons, hydrogen, and if present any unreacted cyclic compounds. ### Claim 15 (depends on 14) The process of claim 14, wherein the cyclic compound composition is a vapor prior to entry into the reaction zone. ### Claim 16 (depends on 14) The process of claim 14, wherein the reaction zone conditions are above the dew point of product stream. ### Claim 17 (depends on 14) The process of claim 14, wherein the cyclic compound composition comprises a cyclic acetal. ### Claim 18 (depends on 14) The process of claim 14, wherein the product stream withdrawn from the reaction zone is a vapor. ### Claim 19 (depends on 14) The process of claim 14, wherein a feed of hydrogen and a feed of cyclic compound composition are in combination within a pipe prior to entry into the reaction zone. ### Claim 20 (depends on 14) The process of claim 14, wherein the reaction in the reaction zone is conducted in the absence of a liquid compound. ### Claim 21 (depends on 14) The process of claim 14, wherein the cyclic acetal comprises the reaction product of a polyhydroxyl compound and an aldehyde. ### Claim 22 (depends on 21) The process of claim 21, wherein the polyhydroxyl compound comprises ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, diethylene glycol, triethylene glycol, or combinations thereof. ### Claim 23 (depends on 21) The process of claim 21, wherein the aldehyde compound comprises acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, pentaldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde, hexyldehyde, benzaldehyde, 2-ethylhexyldehyde, 1,3-cyclohexanedicarboxaldehyde, 1,4-cyclohexanedicarboxaldehyde, or combinations thereof. ### Claim 24 (depends on 21) The process of claim 21, wherein the cyclic acetal comprises 2-propyl-1,3-dioxolane. ### Claim 25 (depends on 21) The process of claim 21, wherein the temperature of the reaction zone is at least 180° C. ### Claim 26 (depends on 21) The process of claim 21, wherein the partial pressure within the reaction zone is above the dew point of all the cyclic compounds within the composition fed to the reaction zone at reaction zone temperature. ### Claim 27 (depends on 1) The process of claim 1, wherein the selectivity to the hydroxy ether compounds is at least 90 mole %.