Attrition resistant supports for fischer-tropsch catalyst and process for making same

Abstract

The invention relates to a novel method of preparing attrition resistance spinel supports for Fischer Tropsch catalysts. The process comprises: (a) combining aluminum oxide, metal compound capable of forming spinel phase, and soluble compound of a trivalent aluminum; (b) mixing the combination resulting in (a) in a manner sufficient to form a slurry comprising the aforementioned combination; and (c) processing the mixture of (b) under conditions sufficient to form metal aluminate spinel composition. Metal aluminate spinel, for example, is formed in the last step by calcining the mixture from (b) at a temperature in the range of 700 to 1300° C., but the process is also capable, of producing attrition resistant supports (e.g., having a DI of 5 or less) at a relatively lower temperature in the range of 700 to 1050° C. The invention also produces the attrition resistance with lower metal loadings than that reported for prior attrition resistant spinel supports.

1 . A process of manufacturing a metal aluminate spinel composition, the process comprising:
 (a) combining aluminum oxide, metal compound capable of forming spinel phase, and soluble compound of a trivalent aluminum;   (b) mixing the combination of (a) under conditions sufficient to form a slurry comprising the aforementioned combination; and   (c) processing the mixture of (b) under conditions sufficient to form metal aluminate spinel composition.   
     
     
         2 . (canceled) 
     
     
         3 . (canceled) 
     
     
         4 . (canceled) 
     
     
         5 . (canceled) 
     
     
         6 . A process according to  claim 1 , wherein the metal compound capable of forming spinel phase is a salt of a divalent metal. 
     
     
         7 . A process according to  claim 6 , wherein the divalent metal is selected from the group consisting of nickel, copper, zinc, cobalt, magnesium and mixture thereof. 
     
     
         8 . A process according to  claim 6 , wherein the divalent metal is selected from the group consisting of zinc, nickel, and magnesium. 
     
     
         9 . A process according to  claim 1 , wherein the soluble compound of trivalent aluminum is selected from the group consisting of aluminum nitrate, aluminum chlorohydrol, aluminum sulfate, aluminum chloride, aluminum acetate, aluminum formate, and mixture thereof. 
     
     
         10 . A process according to  claim 1 , wherein the mixing in (b) comprises intimately mixing the components combined in (a). 
     
     
         11 . A process according to  claim 1 , wherein the mixing in (b) further comprises reducing particle size of solids in the mixture to a median particle size that is less than ten microns. 
     
     
         12 . A process according to  claim 11  wherein the mixing in (b) is without significant gelling. 
     
     
         13 . A process according to  claim 11  wherein the mixing in (b) is conducted in a mill. 
     
     
         14 . A process according to  claim 1 , wherein the mixing in (b) further comprises reducing particle size of solids in the mixture to a median particle size in the range of 1 to 5 microns. 
     
     
         15 . A process according to  claim 1 , wherein (c) comprises drying the mixture from (b) at a temperature in the range of 100 to 400° C. to form particles having a median particle size in the range of 20 to 100 microns and subsequently calcining the particles. 
     
     
         16 . A process according to any one of  claim 15 , wherein (c) comprises drying the mixture from (b) in a spray drier. 
     
     
         17 . A process according to  claim 1 , wherein the processing in (c) comprises calcining the mixture from (b) at a temperature in the range of 700 to 1300° C. 
     
     
         18 . A process according to  claim 17  wherein the processing in (c) comprises calcining the mixture from (b) at a temperature in the range of 700 to 1050° C. 
     
     
         19 . A process according to  claim 17 , wherein product from calcining further comprises alpha alumina. 
     
     
         20 . (canceled) 
     
     
         21 . (canceled) 
     
     
         22 . (canceled) 
     
     
         23 . (canceled) 
     
     
         24 . A metal spinel aluminate prepared by a process comprising
 (a) combining aluminum oxide, metal capable of forming metal spinel compounds, and soluble compound of a trivalent Al;   (b) mixing the combination of (a) sufficient to form a slurry comprising the aforementioned combination; and   (c) processing the mixture of (b) under conditions sufficient to form metal aluminate spinel composition.   
     
     
         25 . A metal spinel aluminate according to  claim 24 , wherein (a) comprises combining (1) aluminum oxide selected from the group consisting of gamma alumina, delta alumina, theta alumina, eta alumina, and mixture thereof; (2) metal capable of forming spinel compounds comprising a salt of a metal, or mixture of metals, other than aluminum; and (3) soluble compound of trivalent Al selected from the group consisting of aluminum nitrate, aluminum chlorohydrol, aluminum sulfate, aluminum chloride, and mixture thereof; (b) comprises reducing the particle size of the solids in the mixture to a median particle size to less than ten microns; and (c) comprises drying the mixture of (b) at a temperature in the range of 100 to 400° C., and calcining the dried mixture at a temperature in the range of 700 to 1300° C. 
     
     
         26 . A metal spinel aluminate according to  claim 25 , wherein (c) comprises drying the mixture from (b) at a temperature in the range of 100 to 400° C. to form particles having a median particle size in the range of 20 to 100 microns prior to calcining. 
     
     
         27 . A metal spinel aluminate according to  claim 24 , having an attrition resistance less than 5 as measured by the Davison Attrition Index.