Self-activating hydroprocessing catalyst having enhanced activity and self-activation characteristics and its use for treating resid feedstocks
View Patent ↗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.
1. A method of making a self-activating hydroprocessing catalyst having enhanced activity, wherein said method comprises:
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 a desired pore structure such that from 50% to 70% of its total pore volume is in pores having a diameter in the range of from 70 Å to 150 Å, at least 20% of the total pore volume is in the pores having a diameter in the range of from 130 Å to 300 Å, and from 3% to 9% of the total pore volume is in the pores having a diameter greater than 1,000 Å, and 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 in the presence of molecular hydrogen to provide said self-activating hydroprocessing catalyst.
2. A method as recited in claim 1 , 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 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 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.
3. A method 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 method as recited in claim 3 , 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.
5. A method 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 weight of the calcined particle based on the molybdenum metal.
6. A method 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 method 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.