'US009670119B2 2) United States Patent (io Patent Noz US 9,670,119 B2 Weiner et al. (45) Date of Patent: *Jun. 6, 2017 (54) PROCESS FOR PRODUCING ETHANOL 370.329 8 1019TY Kaos ea USING MULTIPLE BEDS EACH HAVING BGI28I SUBINTS pins ta DIFFERENT CATALYSTS 3028400 A LBISTS Rech a Roo09s A ALtbte Raton eal (75) Inventors: Hetko Welner, Pasdena, TX (US) Sooetst A "2197 Pave ‘enka Zhou, Houston, 1X (US). 2 is Be Radmila Jevtie, Pasadena, TX (US); oe Victor 4. Johnston, Houston 1X (US) WME Der ta (73) Assignee: CELANESE INTERNATIONAL Gost Gras era CORPORATION, ining, TX US) 2 Stoet Bush cea SSSR Tans ea . fotice: Subject to any disclaimer, the term of this A §I982 Ki ipanja et al (9 Nuee sopewomypetineucemette EGE. he z ‘hho A 519k Ginten USC. 1546) by 0 days ‘deo A oes Sicimn oa Swot A “oe Bow ce This patent is subject to a terminal dis- aoe ee une cea claimer. Sosste AFD var ea ‘Sono A 9m Reet! 21) Appl. No: 157348508 dams Tinetal a kite (22) ids Jam, 1, 2012 ‘ Mesick etal (6) Prior Publication Data 4 Gauthier Lafaye ta US 20121015721 AL Jun. 21,2012 4 Badly a Related U.S. Application Data (Continmed) (3) Cominaton-n-pareof application No. 13094714, FOREIGN PATENT DOCUMENTS fled on Ape 26,2011, and contiauaioninpan of sows application No. 13/178659, ld on Jul 82011. fies (60) Provisional application No, 61/363,056, filed on Jul. EX an 9.2010. x voles 32010 S oiseeos anit G1) Inc a insmwat 110 ee oa oS tt2z9s90 oI core 219 (200601) DE consny eae core 14 (2006.01) atin COTE 29/88 (2006.01) a care 2990 (2006.01) a core ars (2006.01) (OTHER PUBLICATIONS (32) us.cL ‘ergy otal 2007) partion and cise propetics of = CPC. CU7C 29/149 (2013.01): C07C 29/141 imate Sn coment saps NAY ait tse GO13.01}; CO7C 2928 2013.01}, CO7E 29°90 of sucace “ooorncaicshemisay, Apple! Organometallic (2013001), CO7E 678 (2013.01) Chemisty, 2110, SEHD (68) Field of Classiteation Search (Contin) cre core 27104 src = SERB om chu See application fie for compicts search histor mary Examiner — Yong mn ™ " Assistant Examiner — Sonya Wright 6) References Cited (04) Attorney, gen, or Firm — Kilpatick Townsend & USS. PATENT DOCUMENTS. LORDLIG A 121033 Fuchs 207807 A ‘W982 Ford R085 Hamson e a X2985 Hamaon ea. A 7987 Muler eal 411989. ion ‘A Rives Hunter a A 4968 Breck A 101968 Miler ota 3448345 AS19609. Katzen ett S47S1 A 1/1969 Ras tL 3700795 A "L197 Singleton Stockton LLP on The present invention produces ethanol in a stacked bed waetr that comprises a first eatalyst and a sevond eatalyst ‘wherein the frst and second catalysts comprise at least one saoup VIIT metal, and wherein the second catalyst is sub- Stantially free of copper. The crude ethanol product may be separated and ethanol recovered, ABSTRACT 17 Claims, § Drawing SheetsUS 9,670,119 B2 Page 2 66) 450775 Saesae Sante 4476326 Sas0t15 51521 47301 smn ASa1897 asseou an 720 Stross Sizes Soxecot es 190 e207, ison 733 Sires oon 477318 e287 A708 AS00791 4820795 assr307 a8ira0t Sens 4isse.005 0877 961.826 Some ti8 Sossar2 Aovoisss oon'sa2 ‘ookc0s Shoi.299 Stosss 51203908 siiss776 5237.08 S241 05 sbasioos S2a0a71 S2st7se sonss S380751 Shawions Sse9is S390752 $0396 Sats.) S415 741 Sate 592646 Sash) References Cited USS. 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