Zinc(II) and Gallium(III) Catalysts for Olefin Reactions

Abstract

Oligomerization catalyst and method for oligomerization using the catalyst. The catalyst comprises a single Zn(II) or Ga(III) metal ion center directly bonded to a support through a shared oxygen atom, the catalyst having at least one M-O bond which forms an active site for oligomerization. The method includes reacting one or more C2 to C12 olefins with the oligomerization catalyst at a temperature of about 200° C. or higher to provide an oligomer product comprising C4 to C26 olefins.

What is claimed is: 
     
         1 . An oligomerization catalyst, comprising a single Zn(II) metal ion center directly bonded to a support through a shared oxygen atom, the catalyst having at least one Zn—O bond which forms an active site for oligomerization. 
     
     
         2 . The catalyst of  claim 1 , wherein the zinc metal ion has a +2 oxidation state at a temperature of at least 200° C. 
     
     
         3 . The catalyst of  claim 1 , wherein zinc is present in an amount ranging from about 0.1 wt % to about 20 wt %, based on the total weight of the catalyst. 
     
     
         4 . The catalyst of  claim 1 , wherein the support has a surface area of about 30 m 2 /g to about 600 m 2 /g. 
     
     
         5 . The catalyst of  claim 1 , wherein the support has a pore size of about 5 Å to about 500 Å. 
     
     
         6 . The catalyst of  claim 1 , wherein the support is silica oxide, aluminum oxide or silica-aluminum oxide, zeolite, aluminum phosphate molecular sieve, silicon-aluminum phosphate molecular sieve, mesoporous molecular sieve. 
     
     
         7 . A method for making light hydrocarbon oligomers, comprising:
 reacting one or more C2 to C12 olefins with a supported zinc catalyst at a temperature of about 200° C. or higher to provide an oligomer product comprising C4 to C26 olefins, wherein the supported zinc catalyst comprises a single Zn(II) metal ion center directly bonded to a support through a shared oxygen atom, the zinc is present in an amount ranging from about 0.1 wt % to about 20 wt %, based on the total weight of the catalyst.   
     
     
         8 . The method of  claim 7 , wherein the support material is silica having a pore size of about 5 Å to about 500 Å, and a surface area of about 25 m 2 /g to about 600 m 2 /g. 
     
     
         9 . The method of  claim 7 , wherein the one or more C2 to C12 olefins and supported zinc catalyst are reacted at a pressure of about 1 Bar(g) to about 100 Bar(g). 
     
     
         10 . The method of  claim 7 , wherein the one or more C2 to C12 olefins consist essentially of ethylene and propylene. 
     
     
         11 . The method of  claim 7 , wherein the oligomer product consists essentially of C4 to C26 olefins. 
     
     
         12 . The method of  claim 7 , wherein the oligomer product consists essentially of C12 to C20 olefins having a boiling point in the range of 170° C. to 360° C. 
     
     
         13 . An oligomerization catalyst, comprising a single Ga(III) metal ion center directly bonded to a support through a shared oxygen atom, the catalyst having at least one Ga—O bond which forms an active site for oligomerization. 
     
     
         14 . The catalyst of  claim 13 , wherein the gallium metal ion has a +3 oxidation state at a temperature of at least 200° C. 
     
     
         15 . The catalyst of  claim 13 , wherein gallium is present in an amount ranging from about 2 wt % to about 20 wt %, based on the total weight of the catalyst. 
     
     
         16 . The catalyst of  claim 13 , wherein the support has a surface area of about 30 m 2 /g to about 600 m 2 /g. 
     
     
         17 . The catalyst of  claim 13 , wherein the support has a pore size of about 50 Å to about 500 Å. 
     
     
         18 . The catalyst of  claim 13 , wherein the support is silica oxide, aluminum oxide or silica-aluminum oxide. 
     
     
         19 . A method for making light hydrocarbon oligomers, comprising:
 reacting one or more C2 to C12 olefins with a supported gallium containing catalyst at a temperature of about 200° C. or higher to provide an oligomer product comprising C4 to C26 olefins, wherein the supported gallium containing catalyst comprises a single Ga(III) metal ion center directly bonded to a support through a shared oxygen atom, the catalyst having at least one Ga—O bond which forms an active site for oligomerization, and the gallium is present in an amount ranging from about 2 wt % to about 20 wt %, based on the total weight of the catalyst.   
     
     
         20 . The method of  claim 19 , wherein the support material is silica having a pore size of about 50 Å to about 500 Å, and a surface area of about 100 m 2 /g to about 600 m 2 /g. 
     
     
         21 . The method of  claim 19  wherein the one or more C2 to C12 olefins and supported gallium containing catalyst are reacted at a pressure of about 6.8 Bar(g) to about 138 Bar(g). 
     
     
         22 . The method of  claim 19 , wherein the one or more C2 to C12 olefins consist essentially of ethylene and propylene. 
     
     
         23 . The method of  claim 19 , wherein the oligomer product consists essentially of C4 to C26 olefins. 
     
     
         24 . The method of  claim 19 , wherein the oligomer product consists essentially of C12 to C20 olefins having a boiling point in the range of 170° C. to 360° C.