Self-activating hydroprocessing catalyst having enhanced activity and self-activation characteristics and its usefor treating resid feedstocks

Abstract

A self-activating catalyst for treating heavy hydrocarbon feedstocks that comprises a calcined particle treated with a sulfoxide compound in the presence of hydrogen. The calcined particle comprises a co-mulled mixture made by co-mulling inorganic oxide powder, molybdenum trioxide powder, and a nickel compound and then forming the co-mulled mixture into a particle that is calcined to thereby provide the calcined particle. The calcined particle comprises from 1 to 10 weight percent molybdenum and nickel that is present in an amount such that the weight ratio of said nickel-to-molybdenum is less than 0.4. The calcined particle has a pore size distribution that contributes to the unique properties of the catalyst. The enhanced self-activating catalyst is used in the hydroprocessing of heavy residue feedstocks that have high nickel, vanadium and sulfur concentrations.

What is claimed is: 
     
         1 . A self-activating hydroprocessing catalyst for treating heavy hydrocarbon feedstocks, wherein said catalyst comprises:
 a calcined particle treated with a sulfoxide compound in the presence of hydrogen, wherein said calcined particle comprises a co-mulled mixture made by co-mulling inorganic oxide powder, molybdenum trioxide powder, and a nickel compound that is formed into a particle of said co-mulled mixture that is thereafter calcined;   wherein said calcined particle comprises molybdenum in an amount from 1 to 10 weight percent, nickel in an amount such that the weight ratio of nickel-to-molybdenum is less than 0.4; and   wherein said weight percents are for the metal and on the basis of the total weight of the calcined particle.   
     
     
         2 . A self-activating hydroprocessing catalyst as recited in  claim 1 , wherein the treatment of said calcined particle is conducted by contacting said calcined particle with a petroleum-derived hydrocarbon feedstock, having a concentration of said sulfoxide compound such that the sulfur content of said petroleum-derived hydrocarbon feedstock contributed by said sulfoxide compound is in the range of from 0.1 to 8 wt. % of the total weight of the petroleum-derived hydrocarbon feedstock at a LHSV in the range of from 0.01 hr −1  to 10 hr −1  and in the presence of said molecular hydrogen in an amount such that the molar ratio of said molecular hydrogen-to-said petroleum-derived hydrocarbon feedstock is in the range of from 0.1 to 100 moles H 2 /moles hydrocarbon and under treatment conditions such that the treating temperature is in the range of from 120° C. (248° F.) to 370° C. (698° F.) and the treating pressure is in the range of from 250 psia to 2500 psia and for a period of time sufficient to provide said self-activating hydroprocessing catalyst. 
     
     
         3 . A self-activating hydroprocessing catalyst as recited in  claim 2 , wherein said sulfoxide compound is selected from chemical compounds having the following formula: R 1 —S(═O) n —R 2 , wherein,
 R 1  is an alkyl, alkenyl, or alkynyl having from 1 to 4 carbon atoms; 
 R 2  is alkyl, alkenyl, or alkynyl having from 1 to 4 carbon atoms; 
 
       n is either 1 or 2; and
 R 1  and R 2  may or may not be bonded together to form a cyclic molecule. 
 
     
     
         4 . A self-activating hydroprocessing catalyst as recited in  claim 3 , wherein said desire pore structure includes a pore size distribution such that:
 less than 70% of the total pore volume of said calcined particle is in the pores having a diameter in the range of from 70 Å to 150 Å;   at least 10% of the total pore volume of said calcined particle is in the pores having a diameter in the range of from 130 Å to 300 Å; and   from 1% to 10% of the total pore volume of said calcined particle is in the pores having a diameter greater 1,000 Å.   
     
     
         5 . A self-activating hydroprocessing catalyst as recited in  claim 4 , wherein said calcined particle comprises molybdenum in an amount that is at least 2 weight percent and less than 9.5 weight percent of the total particle based on the molybdenum metal. 
     
     
         6 . A self-activating hydroprocessing catalyst as recited in  claim 5 , wherein said calcined particle comprises less than 0.1 weight percent cobalt based as metal and based on the total weight of said calcined particle. 
     
     
         7 . A self-activating hydroprocessing catalyst as recited in  claim 6 , wherein said sulfoxide compound is selected from the group consisting of dimethyl sulfoxide, diethyl sulfide, methyl ethyl sulfoxide, and sulfolane. 
     
     
         8 . A process for hydrotreating a heavy hydrocarbon feedstock, wherein said process comprises:
 contacting under suitable hydroprocessing reaction conditions a self-activating hydroprocessing catalyst, comprising:   a calcined particle treated with a sulfoxide compound in the presence of hydrogen, wherein said calcined particle comprises a co-mulled mixture made by co-mulling inorganic oxide powder, molybdenum trioxide powder, and a nickel compound that is formed into a particle of said co-mulled mixture that is thereafter calcined;   wherein said calcined particle comprises molybdenum in an amount from 1 to 10 weight percent, nickel in an amount such that the weight ratio of nickel-to-molybdenum is less than 0.4; and   wherein said weight percents are for the metal and on the basis of the total weight of the calcined particle.   
     
     
         9 . A process as recited in  claim 8 , wherein the treatment of said calcined particle is conducted by contacting said calcined particle with a petroleum derived hydrocarbon feedstock, having a concentration of said sulfoxide compound such that the sulfur content of said petroleum-derived hydrocarbon feedstock contributed by said sulfoxide compound is in the range of from 0.1 to 8 wt. % of the total weight of the petroleum-derived hydrocarbon feedstock at a LHSV in the range of from 0.01 hr−1 to 10 hr−1 and in the presence of said molecular hydrogen in an amount such that the molar ratio of said molecular hydrogen-to-said petroleum-derived hydrocarbon feedstock is in the range of from 0.1 to 100 moles H2/moles hydrocarbon and under treatment conditions such that the treating temperature is in the range of from 120° C. (248° F.) to 370° C. (698° F.) and the treating pressure is in the range of from 250 psia to 2500 psia and for a period of time sufficient to provide said self-activating hydroprocessing catalyst. 
     
     
         10 . A process as recited in  claim 9 , wherein said sulfoxide compound is selected from chemical compounds having the following formula: R 1 —S(═O) n —R 2 , wherein,
 R 1  is an alkyl, alkenyl, or alkynyl having from 1 to 4 carbon atoms; 
 R 2  is alkyl, alkenyl, or alkynyl having from 1 to 4 carbon atoms; 
 n is either 1 or 2; and 
 R 1  and R 2  may or may not be bonded together to form a cyclic molecule. 
 
     
     
         11 . A process as recited in  claim 10 , wherein said desire pore structure includes a pore size distribution such that:
 less than 70% of the total pore volume of said calcined particle is in the pores having a diameter in the range of from 70 Å to 150 Å;   at least 10% of the total pore volume of said calcined particle is in the pores having a diameter in the range of from 130 Å to 300 Å; and   from 1% to 10% of the total pore volume of said calcined particle is in the pores having a diameter greater 1,000 Å.   
     
     
         12 . A process as recited in  claim 11 , wherein said calcined particle comprises molybdenum in an amount that is at least 2 weight percent and less than 9.5 weight percent of the total particle based on the molybdenum metal. 
     
     
         13 . A process as recited in  claim 12 , wherein said calcined particle comprises less than 0.1 weight percent cobalt based as metal and based on the total weight of said calcined particle. 
     
     
         14 . A process as recited in  claim 13 , wherein said sulfoxide compound is selected from the group consisting of dimethyl sulfoxide, diethyl sulfide, methyl ethyl sulfoxide, and sulfolane. 
     
     
         15 . A self-activating hydroprocessing catalyst having enhanced activity made by a method comprising:
 co-mulling an inorganic oxide powder, finely divided particles of molybdenum trioxide, and a nickel compound to provide a co-mulled mixture;   
       forming said co-mulled mixture into a particle;
 calcining said particle under a controlled temperature condition to provide a calcined particle, having at least 10% but less than 70% of its total pore volume in pores having a diameter in the range of from 70 Å to 150 Å comprising molybdenum in an amount from 1 to 10 weight percent, nickel in an amount such that the weight ratio of nickel-to-molybdenum is less than 0.4; and 
 treating said calcined particle with a sulfoxide compound, selected from the group consisting of dimethyl sulfoxide, diethyl sulfide, methyl ethyl sulfoxide, and in the presence of molecular hydrogen to provide said self-activating hydroprocessing catalyst. 
 
     
     
         16 . A self-activating hydroprocessing catalyst, as recited in  claim 15 , wherein said treating step comprises:
 contacting said calcined particle with a crude oil distillation cut, having a concentration of said sulfoxide compound such that the sulfur content of said crude oil distillation cut contributed by said sulfoxide compound is in the range of from 0.1 to 8 wt. % of the total weight of said crude oil distillation cut at a liquid hourly space velocity (LHSV) in the range of from 0.01 lit′ to 10 lit′ and in the presence of said molecular hydrogen in an amount such that the molar ratio of said molecular hydrogen-to-said crude oil distillation cut is in the range of from 0.1 to 100 moles H 2 /moles hydrocarbon and under treatment conditions such that the treating temperature is in the range of from 120° C. (248° F.) to 370° C. (698° F.) and the treating pressure is in the range of from 250 psia to 2500 psia and for a period of time sufficient to provide said self-activating hydroprocessing catalyst.   
     
     
         17 . A self-activating hydroprocessing catalyst as recited in  claim 16 , wherein said sulfoxide compound is selected from chemical compounds having the following formula: R 1 —S(═O) n —R 2 , wherein,
 R 1  is an alkyl, alkenyl, or alkynyl having from 1 to 4 carbon atoms; 
 R 2  is alkyl, alkenyl, or alkynyl having from 1 to 4 carbon atoms; 
 n is either 1 or 2; and 
 R 1  and R 2  may or may not be bonded together to form a cyclic molecule. 
 
     
     
         18 . A self-activating hydroprocessing catalyst as recited in  claim 17 , wherein said controlled temperature condition includes a calcination temperature is in the range of from about 700° C. to 790° C. for a calcination time period that is effective to provide said calcined particle having said desired pore structure. 
     
     
         19 . A self-activating hydroprocessing catalyst as recited in  claim 18 , wherein said desired pore structure includes a pore size distribution such that:
 from 50% to 70% of the total pore volume of said calcined particle is in the pores having a diameter in the range of from 70 Å to 150 Å;   at least 10% of the total pore volume of said calcined particle is in the pores having a diameter in the range of from 130 Å to 300 Å; and   from 1% to 10% of the total pore volume of said calcined particle is in the pores having a diameter greater 1,000 Å.