Catalyst and process for selective hydrogenation

Abstract

A selective hydrogenation catalyst composition comprises at least two different metal components selected from Groups 8 to 10 of the Periodic Table of Elements, one of which may be rhodium, and at least one metal component selected from Group 13 of the Periodic Table of Elements, such as indium.

1 . A catalyst composition comprising at least two metal components selected from Groups 8 to 10 of the Periodic Table of Elements and at least one metal component selected from Group 13 of the Periodic Table of Elements.  
     
     
         2 . The catalyst composition of  claim 1  wherein one of said at least two metal components selected from Groups 8 to 10 of the Periodic Table of Elements is rhodium.  
     
     
         3 . The catalyst composition of  claim 2  wherein another of said at least two metal components is selected from iron, ruthenium and cobalt.  
     
     
         4 . The catalyst composition of  claim 1  wherein said at least one metal component selected from Group 13 of the Periodic Table of Elements is indium.  
     
     
         5 . The catalyst composition of  claim 1  and further including a binder and/or support.  
     
     
         6 . A catalyst composition comprising: 
 (a) a first component comprising rhodium;    (b) a second component comprising at least one metal selected from Group 13 of the Periodic Table of Elements; and    (c) a third component comprising at least one metal different from said first and second components and selected from Groups 1 to 15 of the Periodic Table of Elements.    
     
     
         7 . The catalyst composition of  claim 6  and further including a support.  
     
     
         8 . The catalyst composition of  claim 7  and comprising from about 0.01 wt % to about 10 wt % of the first component, based on the rhodium metal present by weight of the total weight of the catalyst including the support.  
     
     
         9 . The catalyst composition of  claim 7  and comprising from about 0.04 wt % to about 5 wt % of the first component, based on the rhodium metal present by weight of the total weight of the catalyst including the support.  
     
     
         10 . The catalyst composition of  claim 7  and comprising from about 0.01 wt % to about 30 wt % of the second component, based on the amount of said Group 13 metal present by weight of the total weight of the catalyst including the support.  
     
     
         11 . The catalyst composition of  claim 7  and comprising from about 0.04 wt % to about 20 wt % of the second component, based on the amount of said Group 13 metal present by weight of the total weight of the catalyst including the support.  
     
     
         12 . The catalyst composition of  claim 7  wherein said second component comprises indium.  
     
     
         13 . The catalyst composition of  claim 12  and comprising from about 0.01 wt % to about 20 wt % of the second component, based on the amount of indium metal present by weight of the total weight of the catalyst including the support.  
     
     
         14 . The catalyst composition of  claim 11  and comprising from about 0.04 wt % to about 10 wt % of the second component, based on the amount of indium metal present by weight of the total weight of the catalyst including the support.  
     
     
         15 . The catalyst composition of  claim 7  and comprising from about 0.01 wt % to about 50 wt % of the third component, based on the amount of metal of said third component present by weight of the total weight of the catalyst including the support.  
     
     
         16 . The catalyst composition of  claim 7  and comprising from about 0.05 wt % to about 30 wt % of the third component, based on the amount of metal of said third component present by weight of the total weight of the catalyst including the support.  
     
     
         17 . The catalyst composition of  claim 6  wherein said third component comprises at least one metal selected from Groups 8 to 10 of the Periodic Table of Elements.  
     
     
         18 . The catalyst composition of  claim 6  wherein said third component is selected from iron, ruthenium and cobalt.  
     
     
         19 . The catalyst composition of  claim 7  wherein the third component is iron and the catalyst composition comprises from about 0.05 wt % to about 30 wt % of the third component, based on the amount of iron metal present by weight of the total weight of the catalyst including the support.  
     
     
         20 . The catalyst composition of  claim 7  wherein the third component is iron and the catalyst composition comprises from about 0.1 wt % to about 20 wt % of the third component, based on the amount of iron metal present by weight of the total weight of the catalyst including the support.  
     
     
         21 . The catalyst composition of  claim 7  wherein the third component is cobalt and the catalyst composition comprises from about 0.05 wt % to about 30 wt % of the third component, based on the amount of cobalt metal present by weight of the total weight of the catalyst including the support.  
     
     
         22 . The catalyst composition of  claim 7  wherein the third component is cobalt and the catalyst composition comprises from about 0.1 wt % to about 25 wt % of the third component, based on the amount of cobalt metal present by weight of the total weight of the catalyst including the support.  
     
     
         23 . The catalyst composition of  claim 7  wherein the third component is ruthenium and the catalyst composition comprises from about 0.05 wt % to about 10 wt % of the third component, based on the amount of ruthenium metal present by weight of the total weight of the catalyst including the support.  
     
     
         24 . The catalyst composition of  claim 7  wherein the third component is ruthenium and the catalyst composition comprises from about 0.1 wt % to about 5 wt % of the third component, based on the amount of ruthenium metal present by weight of the total weight of the catalyst including the support.  
     
     
         25 . A catalyst composition comprising: 
 (a) a first component comprising rhodium;    (b) a second component comprising indium; and    (c) a third component selected from one or more of iron, ruthenium and cobalt.    
     
     
         26 . The catalyst composition of  claim 25  and further including a support.  
     
     
         27 . The catalyst composition of  claim 26  and comprising from about 0.01 wt % to about 10 wt % of the first component, based on the rhodium metal present by weight of the total weight of the catalyst including the support.  
     
     
         28 . The catalyst composition of  claim 26  and comprising from about 0.04 wt % to about 5 wt % of the first component, based on the rhodium metal present by weight of the total weight of the catalyst including the support.  
     
     
         29 . The catalyst composition of  claim 26  and comprising from about 0.01 wt % to about 20 wt % of the second component, based on the indium metal present by weight of the total weight of the catalyst including the support.  
     
     
         30 . The catalyst composition of  claim 26  and comprising from about 0.04 wt % to about 10 wt % of the second component, based on the indium metal present by weight of the total weight of the catalyst including the support.  
     
     
         31 . The catalyst composition of  claim 26  wherein the third component is iron and the catalyst composition comprises from about 0.05 wt % to about 30 wt % of the third component, based on the amount of iron metal present by weight of the total weight of the catalyst including the support.  
     
     
         32 . The catalyst composition of  claim 26  wherein the third component is iron and the catalyst composition comprises from about 0.1 wt % to about 20 wt % of the third component, based on the amount of iron metal present by weight of the total weight of the catalyst including the support.  
     
     
         33 . The catalyst composition of  claim 26  wherein the third component is cobalt and the catalyst composition comprises from about 0.05 wt % to about 30 wt % of the third component, based on the amount of cobalt metal present by weight of the total weight of the catalyst including the support.  
     
     
         34 . The catalyst composition of  claim 26  wherein the third component is cobalt and the catalyst composition comprises from about 0.1 wt % to about 25 wt % of the third component, based on the amount of cobalt metal present by weight of the total weight of the catalyst including the support.  
     
     
         35 . The catalyst composition of  claim 26  wherein the third component is ruthenium and the catalyst composition comprises from about 0.05 wt % to about 10 wt % of the third component, based on the amount of ruthenium metal present by weight of the total weight of the catalyst including the support.  
     
     
         36 . The catalyst composition of  claim 26  wherein the third component is ruthenium and the catalyst composition comprises from about 0.1 wt % to about 5 wt % of the third component, based on the amount of ruthenium metal present by weight of the total weight of the catalyst including the support.  
     
     
         37 . The catalyst composition of  claim 25  wherein the molar ratio of rhodium to indium is from about 0.1 to about 1.2.  
     
     
         38 . The catalyst composition of  claim 25  wherein the molar ratio of rhodium to indium is from about 0.3 to about 0.9.  
     
     
         39 . The catalyst composition of  claim 25  wherein the molar ratio of rhodium to the metal of the third component is from about 0.001 to about 0.6.  
     
     
         40 . The catalyst composition of  claim 25  wherein the molar ratio of rhodium to the metal of the third component is from about 0.002 to about 0.3.  
     
     
         41 . The catalyst composition of  claim 26  wherein the support is selected from zirconia, alumina and ceria-alumina.  
     
     
         42 . A method of making a catalyst composition, the method comprising: 
 (a) applying a rhodium compound to a support;    (b) applying a compound of a metal selected from Group 13 of the Periodic Table of Elements to the support; and    (c) applying a compound of a further metal different from rhodium and from said Group 13 metal and selected from Groups 1 to 15 of the Periodic Table of Elements to the support.    
     
     
         43 . The method of  claim 42  wherein said further metal compound is applied to the support before either the rhodium compound or the Group 13 metal compound.  
     
     
         44 . The method of  claim 42  wherein the rhodium compound and the Group 13 metal compound are applied to the support concurrently.  
     
     
         45 . The method of  claim 42  wherein the Group 13 metal compound is applied to the support before the rhodium compound.  
     
     
         46 . The method of  claim 42  wherein the rhodium compound is rhodium nitrate.  
     
     
         47 . The method of  claim 42  wherein the Group 13 metal compound is an indium compound.  
     
     
         48 . The method of  claim 47  wherein the indium compound is indium nitrate or indium formate.  
     
     
         49 . The method of  claim 42  wherein the further metal compound is selected from iron, cobalt and ruthenium compounds.  
     
     
         50 . The method of  claim 42  wherein at least one of the compounds is applied to the support by impregnating the support with a solution of the compound.  
     
     
         51 . The method of  claim 42  wherein at least one of the compounds is applied to the support by precipitating the compound from a solution containing ions of the associated metal.  
     
     
         52 . The method of  claim 42  and, after (a) and/or (b) and/or (c), calcining the support at a temperature of about 100° C. to about 600° C.  
     
     
         53 . The method of  claim 42  and, after (a), (b) and (c), treating the calcined support in a reducing atmosphere at a temperature in excess of 200° C.  
     
     
         54 . A process for selectively removing alkynes or diolefins from a feedstock also containing olefins, the process comprising contacting the feedstock with hydrogen in the presence of a catalyst composition made by the method of  claim 42 .  
     
     
         55 . A process for selectively removing alkynes or diolefins from a feedstock also containing olefins, the process comprising contacting the feedstock with hydrogen in the presence of a catalyst composition comprising at least two different metal components selected from Groups 8 to 10 of the Periodic Table of Elements and at least one metal component selected from Group 13 of the Periodic Table of Elements.  
     
     
         56 . The process of  claim 55  wherein the alkynes or diolefins have 2 to 4 carbon atoms and the feedstock also contains C 2  to C 4  olefins.  
     
     
         57 . A process for selectively removing C 2  to C 4  alkynes or diolefins from a feedstock also containing C 2  to C 4  olefins, the process comprising contacting the feedstock with hydrogen in the presence of a catalyst composition comprising at least two different metal components selected from Groups 8 to 10 of the Periodic Table of Elements and at least one metal component selected from Group 13 of the Periodic Table of Elements, and the process producing an olefin-enriched product stream containing less than 20 weight % oligomerized alkyne and diolefin compounds, based on the weight of said oligomerized alkyne and diolefin compounds in said product stream by the weight of said feedstock.  
     
     
         58 . The process of  claim 57  and producing an olefin-enriched product stream containing less than 10 weight % oligomerized alkyne and diolefin compounds, based on the weight of said oligomerized alkyne and diolefin compounds in said product stream by the weight of said feedstock.  
     
     
         59 . A process for selectively removing alkynes or diolefins from a feedstock also containing olefins, the process comprising contacting the feedstock with hydrogen in the presence of a catalyst composition comprising 
 (a) a first component comprising rhodium;    (b) a second component comprising indium; and    (c) a third component selected from one or more of iron, ruthenium and cobalt.    
     
     
         60 . The process of  claim 59  wherein the alkynes or diolefins have 2 to 4 carbon atoms and the feedstock also contains C 2  to C 4  olefins.  
     
     
         61 . The process of  claim 59  wherein said contacting is conducted at a temperature of from about 20° C. to about 150° C., a pressure of from about 690 kPa to 4100 kPa, and a molar ratio of hydrogen to alkynes and diolefins of from about 1 to about 1000.  
     
     
         62 . The process of  claim 59  wherein said contacting is conducted at a temperature of from about 30° C. to about 100° C., a pressure of from about 1400 kPa to 3400 kPa, and a molar ratio of hydrogen to alkynes and diolefins of from about 1.1 to about 800.