# US 2001/0025129 A1 · Processes for oxidative dehyrogenation > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2001/0025129 A1 - Document ID: US20010025129A1 - Status: Published application - Kind: A1 - Application number: 09/815,914 - Filed: 2001-03-22 - Published: 2001-09-27 - Earliest claimed: 1999-02-22 - Assignees: Symyx Technologies, Inc. - Inventors: Yumin Liu - Web page: https://patentgrep.com/patent/US20010025129A1 ## CPC - C07C 45/34: in unsaturated compounds - B01J 23/002: {Mixed oxides other than spinels, e.g. perovskite} - B01J 23/76: combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 - B01J 23/80: with zinc, cadmium or mercury - B01J 23/83: with rare earths or actinides - B01J 23/847: Vanadium, niobium or tantalum {or polonium} - B01J 23/8474: {Niobium} - B01J 23/8476: {Tantalum} - C07C 5/48: with oxygen as an acceptor - C07C 45/33: of CHx-moieties - C07C 45/35: in propene or isobutene - B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts - C07C 2523/755: Nickel - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS ## Abstract Processes for oxidative dehydrogenation of alkane to one or more olefins, exemplified by ethane to ethylene, are disclosed using novel catalysts. The catalysts comprise a mixture of metal oxides having as an important component nickel oxide (NiO), which give high conversion and selectivity in the process. For example, the catalyst can be used to make ethylene by contacting it with a gas mixture containing ethane and oxygen. The gas mixture may optionally contain ethylene, an inert diluent such as nitrogen, or both ethylene and an inert diluent. ## Claims ### Claim 1 A method comprising contacting at least an alkane having from 2 to 4 carbon atoms to a catalyst comprising at least nickel oxide and dehydrogenating said alkane with a selectivity of greater than 70% and a conversion of greater than 10%. ### Claim 2 (depends on 1) The method of claim 1 wherein said selectivity is greater than 75%. ### Claim 3 (depends on 2) The method of claim 2 wherein said selectivity is greater than 80%. ### Claim 4 (depends on 3) The method of claim 3 wherein said selectivity is greater than 85%. ### Claim 5 (depends on 1) The method of claim 1 wherein said conversion is greater that 15%. ### Claim 6 A process for the oxidative dehydrogenation of an alkane having from 2 to 4 carbon atoms comprising contacting said alkane in the presence of oxygen to a compound comprising nickel oxide and obtaining a selectivity in said dehydrogenation of greater than 70% and a conversion of greater than 10%. ### Claim 7 (depends on 6) The method of claim 6 wherein said selectivity is greater than 75%. ### Claim 8 (depends on 7) The method of claim 7 wherein said selectivity is greater than 80%. ### Claim 9 (depends on 8) The method of claim 8 wherein said selectivity is greater than 85%. ### Claim 10 (depends on 6) The method of claim 6 wherein said conversion is greater that 15%. ### Claim 11 A process for the oxidative dehydrogenation of an alkane having from 2 to 4 carbon atoms comprising contacting a gas mixture comprising said alkane and oxygen to a nickel oxide containing catalyst; and obtaining a selectivity greater than 70% and a conversion greater 10%. ### Claim 12 (depends on 11) The method of claim 11 wherein said selectivity is greater than 75%. ### Claim 13 (depends on 12) The method of claim 12 wherein said selectivity is greater than 80%. ### Claim 14 (depends on 13) The method of claim 13 wherein said selectivity is greater than 85%. ### Claim 15 (depends on 11) The method of claim 11 wherein said conversion is greater that 15%. ### Claim 16 A method for the oxidative dehydrogenation of an alkane having from 2 to 4 carbon atoms comprising contacting said alkane in the presence of oxygen to a material having the empirical formula NixNbyTazOi wherein x is in the range of about 0.05-0.96, y is in the range of from about 0-0.8, z is in the range of from 0-0.8 and i is a number that satisfies valence requirements; and the sum of y and z is at least 0.1. ### Claim 17 (depends on 16) The method of claim 16, wherein x is in the range of from about 0.4 to 0.96. ### Claim 18 (depends on 16) The method of claim 16 wherein x is greater than 0.5. ### Claim 19 (depends on 16) The method of claim 16 wherein y and z are each greater than zero and wherein the sum of y and z is smaller than 0.6. ### Claim 20 A method for the oxidative dehydrogenation of an alkane having from 2 to 4 carbon atoms comprising contacting said alkane in the presence of oxygen to a material having the empirical formula NixAjBkClOi wherein Ni is nickel and x is in the range of about 0.05-0.96; A is a metal selected from the group consisting of Co, Nb, Ta and combinations thereof and j is in the range of from about 0-0.8; B is a dopant selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Mn, La, Ce, Pr, Nd, Sm and combinations thereof and k is in the range of from 0-0.5; C is a dopant selected from the group consisting of Sn, Al, Fe, Si, B, Sb, Tl, In, Ge, Cr, Pb and combinations thereof and l is in the range of from 0-0.5 i is a number that satisfies the valence requirements of the other elements present; and the sum of j, k and l is at least 0.1. ### Claim 21 (depends on 20) The method of claim 20, wherein x is in the range of from about 0.5 to 0.85. ### Claim 22 (depends on 20) The method of claim 20 wherein x is greater than 0.1. ### Claim 23 (depends on 20) The method of claim 20 wherein j, k and l are each greater than zero and wherein the sum of j, k and l is smaller than 0.8. ### Claim 24 A method of making a C2-C4 olefin comprising the step of contacting a gas mixture with a catalyst having an empirical formula: NiaCobNbcTadSneKfAlgFehOi; wherein b, c and d are numbers greater than or equal to zero, but less than one, and at least one of b, c and d is nonzero; e and f are numbers greater than or equal to zero, but less than or equal to 0.35; g and h are numbers greater than or equal to zero, but less than or equal to 0.50; a is a number greater than zero, but less than one, and satisfies: a≦1−b−c−d−e−f−g−h; i is a number that satisfies valence requirements; and the gas mixture comprises a C2-C4 alkane and oxygen. ### Claim 25 (depends on 24) The method of claim 24, wherein: c is greater than or equal to 0.10, but less than or equal to 0.85; and b, d, e, f, g, and h equal zero. ### Claim 26 (depends on 25) The method of claim 25, wherein c is greater than or equal to 0.12, but less than or equal to 0.42. ### Claim 27 (depends on 26) The method of claim 26, wherein c is greater than or equal to 0.14, but less than or equal to 0.25. ### Claim 28 (depends on 25) The method of claim 25, wherein c is greater than or equal to 0.20, but less than or equal to 0.50. ### Claim 29 (depends on 28) The method of claim 28, wherein c is greater than or equal to 0.31, but less than or equal to 0.41. ### Claim 30 (depends on 24) The method of claim 24, wherein: d is greater than or equal to 0.10, but less than or equal to 0.60; and b, c, e, f, g, and h equal zero. ### Claim 31 (depends on 30) The method of claim 30, wherein d is greater than or equal to 0.19, but less than or equal to 0.50. ### Claim 32 (depends on 30) The method of claim 30, wherein d is greater than or equal to 0.14, but less than or equal to 0.25. ### Claim 33 (depends on 24) The method of claim 24, wherein: b is greater than or equal to 0, but less than or equal to 0.20; c is greater than or equal to 0, but less than or equal to 0.80; and d, e, f, g and h equal zero. ### Claim 34 (depends on 33) The method of claim 33, wherein b is greater than or equal to 0.001, but less than or equal to 0.20; and c is greater than or equal to 0.02, but less than or equal to 0.56. ### Claim 35 (depends on 33) The method of claim 33, wherein b is greater than or equal to 0, but less than or equal to 0.30; and c is greater than or equal to 0, but less than or equal to 0.45. ### Claim 36 (depends on 35) The method of claim 35, wherein a is greater than or equal to 0.55, but less than or equal to 0.85. ### Claim 37 (depends on 33) The method of claim 33, wherein: b is greater than or equal to 0, but less than or equal to 0.33; and c is greater than or equal to 0, but less than or equal to 0.52. ### Claim 38 (depends on 37) The method of claim 37, wherein: b is less than or equal to 0.10; and c is greater than or equal to 0.20, but less than or equal to 0.50. ### Claim 39 (depends on 37) The method of claim 37, wherein: b is less than or equal to 0.03; and c is less than or equal to 0.50. ### Claim 40 (depends on 39) The method of claim 39, wherein c is greater than or equal to 0.15, but less than or equal to 0.26. ### Claim 41 (depends on 37) The method of claim 37, wherein: b is greater than or equal to 0.001, but less than or equal to 0.19; and c is greater than or equal to 0.13, but less than or equal to 0.33. ### Claim 42 (depends on 41) The method of claim 41, wherein c is less than or equal to 0.23. ### Claim 43 (depends on 24) The method of claim 24, wherein: c is greater than or equal to 0, but less than or equal to 0.50; d is greater than or equal to 0, but less than or equal to 0.50; and b, e, f, g and h equal zero. ### Claim 44 (depends on 43) The method of claim 43, wherein: c is greater than or equal to 0.03, but less than or equal to 0.40; and d is greater than or equal to 0.02, but less than or equal to 0.29. ### Claim 45 (depends on 43) The method of claim 43, wherein: a is greater than or equal to 0.46, but less than or equal to 0.96; c is greater than or equal to 0.04, but less than or equal to 0.44; and d is greater than or equal to 0.04, but less than or equal to 0.44. ### Claim 46 (depends on 45) The method of claim 45, wherein: a is greater than or equal to 0.54, but less than or equal to 0.72; c is greater than or equal to 0.04, but less than or equal to 0.38; and d is greater than or equal to 0.04, but less than or equal to 0.40. ### Claim 47 (depends on 46) The method of claim 46, wherein: a is less than or equal to 0.65; c is less than or equal to 0.20; and d is greater than or equal to 0.15. ### Claim 48 (depends on 24) The method of claim 24, wherein: c, d and e are each greater than or equal to 0, but less than or equal to 0.35; and b, f, g and h equal zero. ### Claim 49 (depends on 24) The method of claim 24, wherein: c, d and f are each greater than or equal to 0, but less than or equal to 0.35; and b, e, g and h equal zero. ### Claim 50 (depends on 46) The method of claim 46, wherein: a is greater than or equal to 0.58, but less than or equal to 0.64; c is greater than or equal to 0.06, but less than or equal to 0.38; d is greater than or equal to 0.04, but less than or equal to 0.30; and f is less than or equal to 0.26. ### Claim 51 (depends on 47) The method of claim 47, wherein: a is greater than or equal to 0.55, but less than or equal to 0.65; c is greater than or equal to 0.30, but less than or equal to 0.40; and b, d, e, and f equal zero. ### Claim 52 (depends on 51) The method of claim 51, wherein: a is greater than or equal to 0.58, but less than or equal to 0.61; c is greater than or equal to 0.35, but less than or equal to 0.36; g is greater than or equal to 0, but less than or equal to 0.05; and h is greater than or equal to 0, but less than or equal to 0.07. ### Claim 53 (depends on 24) The method of claim 24, wherein the gas mixture further comprises a material selected from the group consisting of ethylene, butylenes or raffinate II. ### Claim 54 (depends on 24) The method of claim 24, wherein said contacting is carried out at a temperature of about 400° C. or less. ### Claim 55 (depends on 24) The method of claim 24, wherein the contacting step is carried out at a temperature of about 325° C. or less. ### Claim 56 (depends on 24) The method of claim 24, wherein the contacting step is carried out at a temperature of about 300° C. or less. ### Claim 57 (depends on 24) The method of claim 24, wherein said catalyst is not supported on a carrier. ### Claim 58 (depends on 24) The method of claim 24, wherein said catalyst is supported on a carrier selected from the group consisting of silica, alumina, titania, zirconia, magnesia, zeolites, clays and combinations thereof. ### Claim 59 (depends on 24) The method of claim 24 wherein said contacting is carried out for a time in the range of from about 100 milliseconds to about 10 seconds. ### Claim 60 (depends on 24) The method of claim 24, wherein said gas mixture comprises oxygen in the range of from about 0.01-20% by volume and ethane in the range of from about 10-99.99% by volume. ### Claim 61 (depends on 60) The method of claim 60, wherein said gas mixture further comprises diluents in the range of from about 0.01-60% by volume. ### Claim 62 (depends on 60) The method of claim 60, wherein said reaction pressure is in the range of from 0.5 to 20 bar. ### Claim 63 (depends on 24) The method of claim 24, wherein said catalyst is diluted with a binder or inert filler. ### Claim 64 (depends on 24) The method of claim 24 wherein said catalyst is calcined at a temperature of 400° C. or less. ### Claim 65 (depends on 24) The method of claim 24 wherein said catalyst is calcined at a temperature of 350° C. or less. ### Claim 66 (depends on 24) The method of claim 24 wherein said catalyst is calcined at a temperature of 300° C. or less. ### Claim 67 A method for the oxidative dehydrogenation of ethane to ethylene, optionally with ethylene as a co-feed with said ethane, comprising contacting ethane to a catalyst comprising nickel oxide (NiO) with either niobium oxide (Nb2O5) or tantalum oxide (Ta2O5).