High activity hydrodesulfurization catalyst, a method of making a high activity hydrodesulfurization catalyst, and a process for manufacturing an ultra-low sulfur distillate product

Abstract

A method of making a high activity catalyst composition suitable for use in the hydrodesulfurization of a middle distillate feed, such as diesel fuel, having a high concentration of sulfur, to thereby provide a low sulfur middle distillate product. The method comprises heat treating aluminum hydroxide under controlled temperature conditions thereby converting said aluminum hydroxide to gamma-alumina to give a converted aluminum hydroxide, and controlling the fraction of said converted aluminum hydroxide that is gamma-alumina by controlling said controlled temperature conditions to within a calcination temperature range of from 850° F. (454° C.) to 950° C. (510° C.) so that essentially all of said aluminum hydroxide is converted to a transition alumina but less than a material amount of the converted aluminum hydroxide is converted to a transition alumina other than gamma-alumina. A catalytic component is incorporated into said converted aluminum hydroxide to provide an intermediate, which is heat treated to provide said high activity catalyst composition. The high activity catalyst composition can, thus, comprises gamma-alumina and a catalytic component, but having a material absence of aluminum hydroxide and a phase of a transition alumina other than gamma-alumina. Another embodiment of the high activity catalyst composition comprises a support material consisting essentially of gamma-alumina and a catalytic component. The high activity catalyst composition can suitably be used in the hydrodesulfurization of a middle distillate feed containing a high sulfur concentration.

1 . A method of making a catalyst composition suitable for use in the manufacture of ultra low sulfur diesel, said method comprises: 
 forming a shaped particle comprising at least 90 weight percent, exclusive of water, boehmite;    heat treating said shaped particle under a controlled temperature condition to convert said boehmite of said shaped particle to gamma-alumina; controlling said controlled temperature condition to within a calcination temperature range of from about 850° F. and 950° F. so as to convert said boehmite to a crystalline transitional phase of alumina thereby providing a heat treated shaped particle;    incorporating a hydrogenation catalytic component into said heat treated shaped particle to thereby provide an impregnated heat treated shaped particle; and    heat treating said impregnated heat treated shaped particle to thereby provide said catalyst composition.    
   
   
       2 . A method as recited in  claim 1 , wherein said controlled temperature condition provides for the conversion of essentially all but a non-material amount of said boehmite of said shaped particle to be converted to a transitional crystalline phase of alumina.  
   
   
       3 . A method as recited in  claim 2 , wherein said controlled temperature condition further provides for said transitional crystalline phase that comprises gamma alumina and further wherein said transitional crystalline phase includes a material absence of said transitional crystalline phase of alumina other than gamma alumina.  
   
   
       4 . A method as recited in  claim 3 , wherein said heat treated shaped particle contains less than 5 weight percent boehmite with the weight percent being based on the total weight of said heat treated shaped particle.  
   
   
       5 . A method as recited in  claim 4 , wherein less than 5 weight percent of said alumina of said heat treated shaped particle is said transitional crystalline phase of alumina other than gamma alumina.  
   
   
       6 . A method as recited in  claim 5 , wherein the median pore diameter of said heat treated shaped particle is in the range of from about 70 angstroms to about 120 angstroms, wherein the total pore volume of said heat treated shaped particle is in the range of from about 0.5 cc/gram to about 1.1 cc/gram, and wherein more than 70 percent of the total pore volume of said heat treated shaped particle is contained in the pores having a pore diameter of from 70 angstroms to 350 angstroms.  
   
   
       7 . A method as recited in  claim 6 , wherein said hydrogenation catalytic component is selected from the group of consisting of molybdenum compounds, cobalt compounds, nickel compounds, phosphorous compounds, and any combination of one or more of such compounds.  
   
   
       8 . A method as recited in  claim 7 , wherein said heat treating of said impregnated heat treated shaped particle is conducted so that the at least 90 weight percent of the alumina of said catalyst composition is in the crystalline transitional phase of gamma alumina and less than 5 weight percent of the alumina of said catalyst composition is in the crystalline transitional phase other than gamma alumina.  
   
   
       9 . A method as recited in  claim 8 , wherein said catalyst composition is characterized as having a median pore diameter in the range of from about 80 angstroms to about 110 angstroms, a total pore volume in the range of from about 0.6 cc/gram to about 1.1 cc/gram, and more than 70 percent of said total pore volume that is contained in the pores having a pore diameter of from 80 angstroms to 350 angstroms.  
   
   
       10 . A method as recited in  claim 9 , wherein said catalyst composition further comprises a molybdenum compound in the range of from about 3 to about 30 weight percent, calculated as molybdenum trioxide, a cobalt compound in the range of from about 0.01 to about 10 weight percent, calculated as cobalt oxide, and a phosphorous compound in the range of from about 0.01 weight percent to about 5 weight percent, calculated as phosphorous.  
   
   
       11 . A method of making a catalyst composition suitable for use in the manufacture of ultra low sulfur diesel, said method comprises: 
 forming a shaped particle comprising at least 90 weight percent, exclusive of water, boehmite;    calcining said shaped particle under a controlled temperature condition to convert said boehmite of said shaped particle to gamma-alumina; controlling said controlled temperature condition to within a calcination temperature range of from about 850° F. and 950° F. so that a substantial portion of said boehmite of said shaped particle is converted to a crystalline transitional phase of alumina but less than a material amount of said boehmite of said shaped particle is converted to a crystalline transitional phase other than gamma-alumina to thereby provide a calcined shaped particle;    impregnating said calcined shaped particle with a hydrogenation catalytic component to thereby provide an impregnated calcined shaped particle; and    calcining said impregnated calcined shaped particle to thereby provide said catalyst composition.    
   
   
       12 . A method as recited in  claim 11 , wherein said calcined shaped particle has a material absence of both boehmite and a crystalline transitional phase of alumina other than gamma-alumina.  
   
   
       13 . A method as recited in  claim 12 , wherein said calcined shaped particle contains less than 5 weight percent boehmite with the weight percent being based on the total weight of said calcined shaped particle.  
   
   
       14 . A method as recited in  claim 13 , wherein less than 5 weight percent of said alumina of said calcined shaped particle is said transitional crystalline phase of alumina other than gamma alumina.  
   
   
       15 . A method as recited in  claim 14 , wherein the median pore diameter of said calcined shaped particle is in the range of from about 80 angstroms to about 110 angstroms, wherein the total pore volume of said calcined shaped particle is in the range of from about 0.6 cc/gram to about 1.1 cc/gram, and wherein more than 70 percent of the total pore volume of said calcined shaped particle is contained in the pores having a pore diameter of from 80 angstroms to 350 angstroms.  
   
   
       16 . A method as recited in  claim 15 , wherein said hydrogenation catalytic component is selected from the group of consisting of molybdenum compounds, cobalt compounds, nickel compounds, phosphorous compounds, and any combination of one or more of such compounds.  
   
   
       17 . A method as recited in  claim 16 , wherein said calcining of said impregnated calcined shaped particle is conducted so that the at least 90 weight percent of the alumina of the resulting said catalyst composition is in the crystalline transitional phase of gamma alumina and less than 5 weight percent of the alumina of said catalyst composition is in the crystalline transitional phase other than gamma alumina.  
   
   
       18 . A method as recited in  claim 17 , wherein said catalyst composition is characterized as having a median pore diameter in the range of from about 80 angstroms to about 110 angstroms, a total pore volume in the range of from about 0.6 cc/gram to about 1.1 cc/gram, and more than 70 percent of said total pore volume that is contained in the pores having a pore diameter of from 80 angstroms to 350 angstroms.  
   
   
       19 . A method as recited in  claim 18 , wherein said catalyst composition further comprises a molybdenum compound in the range of from about 2 to about 10 weight percent, calculated as molybdenum trioxide, a cobalt compound in the range of from about 0.01 to about 10 weight percent, calculated as cobalt oxide, and a phosphorous compound in the range of from about 0.01 weight percent to about 5 weight percent, calculated as phosphorous.  
   
   
       20 . A method, comprising: 
 providing a shaped support, having a material absence of aluminum hydroxide and a material absence of a crystalline transitional phase of alumina other than gamma-alumina;    incorporating a catalytic component into said shaped support to thereby provide an intermediate; and    calcining said intermediate to thereby provide a catalyst composition comprising said catalytic component and alumina wherein less than 5 weight percent of said alumina is a crystalline transitional alumina phase other than gamma alumina.    
   
   
       21 . A method as recited in  claim 20 , wherein said material absence of aluminum hydroxide in said shaped support is less than 5 weight percent of the total weight of said shaped support that is aluminum hydroxide and wherein said material absence of said crystalline transitional phase of alumina other than gamma alumina in said shaped support is less than 5 weight percent of the total weight of said shaped support that is said crystalline transitional phase of alumina other than gamma alumina.  
   
   
       22 . A method as recited in  claim 21 , wherein less than 2 weight percent of said alumina is a crystalline transitional alumina phase other than gamma alumina.  
   
   
       23 . A method as recited in  claim 22 , wherein less than 1 weight percent of said alumina is a crystalline transitional alumina phase other than gamma alumina.  
   
   
       24 . A method as recited in  claim 23 , wherein said catalytic component incorporated into said shaped support is such as to provide said catalyst composition that further comprises a molybdenum compound in the range of from about 2 to about 10 weight percent, calculated as molybdenum trioxide, a cobalt compound in the range of from about 0.01 to about 10 weight percent, calculated as cobalt oxide, and a phosphorous compound in the range of from about 0.01 weight percent to about 5 weight percent, calculated as phosphorous.  
   
   
       25 . A catalyst composition, comprising: 
 a calcined impregnated shaped support, wherein said shaped support of said impregnated shaped support has a material absence of aluminum hydroxide and a material absence of crystalline transitional phase of alumina other than gamma-alumina prior to the impregnation thereof with a hydrogenation catalytic component to thereby provide said impregnated shaped support thereafter calcined.    
   
   
       26 . A catalyst composition as recited in  claim 25 , wherein said material absence of aluminum hydroxide in said shaped support is less than 5 weight percent of the total weight of said shaped support and wherein said material absence of said crystalline transitional phase of alumina other than gamma alumina in said shaped support is less than 5 weight percent of the total weight of said shaped support.  
   
   
       27 . A catalyst composition as recited in  claim 26 , wherein said material absence of said crystalline transitional phase of alumina other than gamma alumina is less than 2 weight percent of the total weight of said shaped support.  
   
   
       28 . A catalyst composition as recited in  claim 27 , wherein said material absence of said crystalline transitional phase of alumina other than gamma alumina is less than 1 weight percent of the total weight of said shaped support.  
   
   
       29 . A catalyst as recited in  claim 28 , wherein said hydrogenation catalytic component in said catalyst composition includes a molybdenum compound in the range of from about 3 to about 30 weight percent, calculated as molybdenum trioxide, a cobalt compound in the range of from about 0.01 to about 10 weight percent, calculated as cobalt oxide, and a phosphorous compound in the range of from about 0.01 weight percent to about 5 weight percent, calculated as phosphorous, wherein the weight percents are based on the total weight of said catalyst composition.  
   
   
       30 . A catalyst as recited in  claim 29 , wherein said catalyst composition is characterized as having a median pore diameter in the range of from about 80 angstroms to about 110 angstroms, a total pore volume in the range of from about 0.6 cc/gram to about 1.1 cc/gram, and more than 70 percent of said total pore volume that is contained in the pores having a pore diameter of from 80 angstroms to 350 angstroms.  
   
   
       31 . A catalyst composition suitable for use in the hydrodesufurization of a middle distillate feedstock having a concentration of sulfur to yield a ultra low sulfur middle distillate product, said catalyst composition comprises: 
 a calcined impregnated shaped support, wherein said shaped support of said impregnated shaped support comprises, prior to its impregnation and calcination, at least 90 weight percent alumina that is in the crystalline transitional phase of gamma-alumina, less than 5 weight percent alumina that is in the crystalline transitional phase of delta-alumina, and less than 5 weight percent alumina that is in the crystalline transitional phase other than gamma-alumina and delta-alumina, and wherein said shaped support has incorporated therein a hydrogenation catalytic component thereby providing said impregnated shaped support, and wherein said impregnated shaped support is calcined.    
   
   
       32 . A catalyst composition as recited in  claim 31 , having less than 2 weight percent alumina that is in the crystalline transitional phase other than gamma alumina.  
   
   
       33 . A catalyst composition as recited in  claim 32 , having less than 1 weight percent alumina that is in the crystalline transitional phase other than gamma alumina.  
   
   
       34 . A catalyst as recited in  claim 33 , wherein said hydrogenation catalytic component in said catalyst composition includes a molybdenum compound in the range of from about 3 to about 30 weight percent, calculated as molybdenum trioxide, a cobalt compound in the range of from about 0.01 to about 10 weight percent, calculated as cobalt oxide, and a phosphorous compound in the range of from about 0.01 weight percent to about 5 weight percent, calculated as phosphorous, wherein the weight percents are based on the total weight of said catalyst composition.  
   
   
       35 . A catalyst as recited in  claim 34 , wherein said catalyst composition is characterized as having a median pore diameter in the range of from about 80 angstroms to about 110 angstroms, a total pore volume in the range of from about 0.6 cc/gram to about 1.1 cc/gram, and more than 70 percent of said total pore volume that is contained in the pores having a pore diameter of from 80 angstroms to 350 angstroms.  
   
   
       36 . A catalyst composition, comprising: 
 a support material comprising, exclusive of catalytic components, alumina comprising more than 90 weight percent gamma alumina and less than 5 weight percent crystalline transitional phase other than gamma alumina; and catalytic components including a molybdenum compound in the range of from about 2 to about 10 weight percent, calculated as molybdenum trioxide, a cobalt compound in the range of from about 0.01 to about 10 weight percent, calculated as cobalt oxide, and a phosphorous compound in the range of from about 0.01 weight percent to about 5 weight percent, calculated as phosphorous, wherein the weight percents are based on the total weight of said catalyst composition; and wherein said catalyst composition is characterized as having a median pore diameter in the range of from about 80 angstroms to about 110 angstroms, a total pore volume in the range of from about 0.6 cc/gram to about 1.1 cc/gram, and more than 70 percent of said total pore volume that is contained in the pores having a pore diameter of from 80 angstroms to 350 angstroms.    
   
   
       37 . A catalyst made by the methods of claims  1  through  24 .  
   
   
       38 . A process for making an ultra low sulfur diesel product, said process comprises: 
 contacting, under hydrodesulfurization conditions, a diesel feedstock, wherein said diesel feedstock comprises a first sulfur concentration, with a catalyst composition of any one of claims  25  through  36 ; and yielding said ultra low sulfur diesel product having a second sulfur concentration.    
   
   
       39 . A process, comprising: 
 contacting under hydrodesulfurization conditions a middle distillate feedstock having a high sulfur concentration with a catalyst composition of any one of claims  25  through  36  and yielding an ultra low sulfur middle distillate feedstock having a ultra low sulfur concentration.