US009221727B2 (12) United States Patent (10) Patent No.: US 9.221,727 B2 Cheung et al. (45) Date of Patent: Dec. 29, 2015 (54) SELECTIVE HYDROGENATION CATALYST USPC .......... 585/269,277: 502/162, 164, 262,327, AND METHODS OF MAKING AND USING 502/328,330, 333,339, 439 SAME See application file for complete search history. (56) References Cited (71) Applicant: Chevron Phillips Chemical Company LP, The Woodlands, TX (US) U.S. PATENT DOCUMENTS (72) Inventors: Tin-Tack Peter Cheung, Kingwood, TX 3,463,830 A 8/1969 Dunning et al. (US); Zongxuan Hong, Houston, TX 3,625,755 A 12, 1971 Potrafike (US) (Continued) (73) Assignee: Chevron Phillips Chemical Company FOREIGN PATENT DOCUMENTS LP, The Woodlands, TX (US) CN 1422695 A 6, 2003 (*) Notice: Subject to any disclaimer, the term of this CN 1425,637 A 6, 2003 patent is extended or adjusted under 35 (Continued) U.S.C. 154(b) by 0 days. OTHER PUBLICATIONS (21) Appl. No.: 14/669,541 Boitiaux, J.P. et al., “Hydrogenation of highly unsaturated hydrocar bons over highly dispersed Pd catalyst. Part II: Ligand effect of (22) Filed: Mar. 26, 2015 piperidine.” Applied Catalysis, 1985, vol. 15, pp. 317-326, Elsevier Science Publishers B.V., Amsterdam, XPOO2577931. (65) Prior Publication Data (Continued) US 2015/O197464 A1 Jul. 16, 2015 Primary Examiner — Cam N. Nguyen (74) Attorney, Agent, or Firm — Conley Rose, P.C.; Rodney Related U.S. Application Data B. Carroll; Lynda Jolly (62) Division of application No. 14/134,282, filed on Dec. (57) ABSTRACT 19, 2013, now Pat. No. 9,012,348, which is a division A composition comprising a Supported hydrogenation cata of application No. 12/710,781, filed on Feb. 23, 2010, lyst comprising palladium and an organophosphorous com now Pat. No. 8,633,127. pound, the Supported hydrogenation catalyst being capable of (60) Provisional application No. 61/157,491, filed on Mar. selectively hydrogenating highly unsaturated hydrocarbons 4, 2009. to unsaturated hydrocarbons. A method of making a selective hydrogenation catalyst comprising contacting a Support with (51) Int. C. a palladium-containing compound to form a palladium Sup C07C 5/10 (2006.01) ported composition, contacting the palladium Supported BOI.3L/00 (2006.01) composition with an organophosphorus compound to form a (Continued) catalyst precursor, and reducing the catalyst precursor to form the catalyst. A method of selectively hydrogenating highly (52) U.S. C. unsaturated hydrocarbons to an unsaturated hydrocarbon CPC. C07C5/09 (2013.01); B01J 23/44 (2013.01); enriched composition comprising contacting a Supported B01J 23/66 (2013.01); B01J 27/13 (2013.01); catalyst comprising palladium and an organophosphorous (Continued) compound with a feed comprising highly unsaturated hydro (58) Field of Classification Search carbon under conditions suitable for hydrogenating at least a CPC ............. C07C 5/10; B01J 31/24: B01J 31/26; portion of the highly unsaturated hydrocarbon feed to form B01J 31/28: B01J 23/44; B01J 23/56; B01J the unsaturated hydrocarbon enriched composition. 23/58 21 Claims, 2 Drawing Sheets 10 20 US 9,221,727 B2 Page 2 (51)51) Int. Cl. 6,603,038 B1 8/2003 Hagemevergemey et al. 6,635,600 B1 10/2003 Kimble et al. BOI 2L/00 (2006.01) 6,821.412 B1 1 1/2004 Fujukawa et al. BOI 2L/04 (2006.01) 6,831,035 B2 12/2004 Puckette et al. BOI. 23/00 (2006.01) 6,852,661 B1 2/2005 Ahlers et al. BOI. 23/02 (2006.01) 6,969,694 B2 11/2005 Zhang 7,148,176 B2 12/2006 Beller et al. BOI. 23/240 (2006.01) 7,160,835 B2 1/2007 Tsuji BOI. 23/242 (2006.01) 7,408,089 B2 8/2008 Ryu BOI. 23/44 (2006.01) 7,417,007 B2 * 8/2008 Cheung .................... B01J 23.44 BOI. 23/58 (2006.01) 502,208 C07C5/09 (2006.01) 7,586,010 B2 9, 2009 Liu et al. 7,704,912 B2 4/2010 Reetz et al. BOI. 23/66 (2006.01) 7,737,075 B2 6/2010 Ryu BOI 27/3 (2006.01) 7,737,079 B2 6/2010 Ryu BOI 3/16 (2006.01) 7.919,431 B2 * 4/2011 Johnson ................... BO1J 23.50 BOI 3/18 (2006.01) 8,633,127 B2 1/2014 Ch 1 502,324 w - - eung et al. SE7 3.08: 8,729,326 B2 * 5/2014 Cheung.................... B01J 23.44 502/230 BOI. 37/28 (2006.01) 9.012,348 B2 4/2015 Cheung et al. CIOG 45/40 (2006.01) 2003/0144139 A1 7/2003 Shimizu et al. BOI.3L/02 (2006.01) 2003/O15827O A1 8/2003 Mahajan 2003/0228977 A1 12/2003 Yokozawa et al. C07C ". (2006.01) 2004/0092388 A1 5/2004 Shimizu et al. BOIJ 35/OO (2006.01) 2004/O138056 A1 7, 2004 Zhao et al. BOIJ 35/02 (2006.01) 2004/0192983 A1 9/2004 Bergmeister et al. BOIJ 35/IO (2006.01) 2004/026012.6 A1 12/2004 Augustine et al. (52) U.S. Cl. 2007/0027030 Al 22007 Cheung et al. CPC .......... Bot to 71 (2013.01). Botvi/161, 200706183 Al 72007 Bergmeister, III et al. (2013.01); B01J 31/185 (2013.01); B01.J FOREIGN PATENT DOCUMENTS 31/1845 (2013.01); B01J 31/1865 (2013.01); B01J 31/1875 (2013.01); B01J 31/24 CN 102341,175. A 2, 2012 (2013.01); B01J 3 1/2404 (2013.01); B01.J EP O933129 A1 8, 1999 EP 2403642 A2 1, 2012 370203 (2013.01); B01J 37/28 (2013.01): JP O8066633. A 3, 1996 C07C5/05 (2013.01); C10G 45/40 (2013.01); JP O9000937 A 1, 1997 B01J 35/008 (2013.01); B01.J35/023 (2013.01); JP 2007518676 A 7/2007 B01.J35/1009 (2013.01); B01.J35/1014 WO OO23403 A1 4/2000 (2013.01); B01J 37/024 (2013.01); B01.J WO 2005.000773 A1 1, 2005 223 1/645 (2013.01); B01J 2531/824 (2013.01); WO 2010101736 A2 9, 2010 C07C 2521/04 (2013.01); C07C 2531/26 WO 2010101736 A3 9, 2010 (2013.01); C10G 2300/703 (2013.01) OTHER PUBLICATIONS (56) References Cited Database, WPI. Week 200365, Thompson Scientific, London, GB, 2003-680539, CN1425637A, Jun. 25, 2003, 1 page, XP002577876. U.S. PATENT DOCUMENTS Kwon, Min Serk, et al., “Palladium nanoparticles entrapped in alu 3,635,841 A 1/1972 Keith et al. minum hydroxide: dual catalyst for alkene hydrogenation and aero 3,947.495 A 3, 1976 Murib et al. bic alcohol oxidation.” Organic Letters, 2005, vol. 7, No. 6, pp. 4,120,901 A 10, 1978 Hobbs et al. 1077-1079, American Chemical Society, XP002577877. 4,204,997 A 5, 1980 Hobbs et al. Song, Choong Eui, et al., “Supported chiral catalysts on inorganic 4.325,834 A 4, 1982 Bartish et al. materials.” Chem. Rev., 2002, vol. 102, pp. 3495-3524. American 4,384,981 A 5, 1983 Dines et al. Chemical Society, XP002297471. 4.404,124 A 9, 1983 Johnson et al. UOP Method 578-02, “Automated Pore Volume and Pore Size Dis 4.418,227 A * 1 1/1983 Pez ........................ B01J 31,121 568,861 tribution of Porous Substances by Mercury Porosimetry.” UOPLLC, 4.484.015 A 11, 1984 Johnson et al. 1984, pp. 1-14. 4,713,363 A 12, 1987 Hucul Westermark, Gunnar, et al., “An infrared study on the chemisorption 4,774,221 A 9, 1988 Medem et al. of tertiary phosphines on coinage and platinum group metal Sur 4,786,623 A 11, 1988 Grenouillet et al. faces.” Colloids and Surfaces A: Physicochemical and Engineering 4,889,949 A 12/1989 Grenouillet et al. Aspects, 1999, vol. 150, pp. 31-43, Elsevier Science, B.V. 5,028,576 A 7, 1991 Drent et al. Westermark, Gunnar, et al., “Chemisorption of tertiary phosphines 5,113,022 A 5/1992 Abatjoglou et al. 5,166,116 A 11/1992 Drent et al. on coinage and platinum group metal powders. An infrared reflec 5,189,003 A 2f1993 Klusener et al. tance absorption spectroscopic, enhanced Raman spectroscopic and 5,482.596 A 1, 1996 Wu surface coverage study.” Colloids and Surfaces A: Physicochemical 5,712.403 A 1/1998 Sato et al. and Engineering Aspects, 1998, vol. 144, pp. 149-166, Elsevier Sci 5,880,301 A 3, 1999 Shibasaki et al. ence B.V. 6,005,123 A 12/1999 Dessau et al. Filing Receipt and provisional patent specification entitled "Selective 6,127.588 A * 10/2000 Kimble .................... B01J 23.44 585,259 hydrogenation catalyst and methods of making and using same.” by 6,140,265 A 10, 2000 Haber et al. Tin-Tack Peter Cheung, et al., filed Mar. 4, 2009 as U.S. Appl. No. 6, 197,716 B1 3/2001 Baumeister et al. 61/157,491. 6, 197,720 B1 3, 2001 Heineke et al. Foreign communication from a related counterpart application— 6,232,262 B1 5, 2001 Sielcken et al. Invitation to Pay Additional Fees, PCT/US2010/025.038, 9 pages, 6,541,417 B2 4/2003 Kasztelan et al. Jun. 14, 2010. US 9,221,727 B2 Page 3 (56) References Cited Foreign communication from a related counterpart application— Australian Examination Report, Application No. 2010221662, Oct. OTHER PUBLICATIONS 8, 2014, 3 pages. Foreign communication from a related counterpart application— Foreign communication from a related application—International Philippines Examination Report, Application No. 1201 1501710, Search Report and Written Opinion, PCT/US2010/025038, Nov. 26, Feb. 5, 2015, 1 page. Foreign communication from a related counterpart application— 2010, 18 pages. Australian Examination Report, Application No. 201320 1876, Oct. Foreign communication from a related counterpart application— 15, 2014, 3 pages.