Hydrocracking catalysts, processes for preparing the same and uses thereof

Abstract

Provided are hydrocracking catalysts comprising a cracking component and a hydrogenation component, wherein, for example: the cracking component comprises at least one molecular sieve present in an amount ranging from 0% to 20% by weight relative to the total weight of the catalyst and at least one amorphous silica-alumina present in an amount ranging from 20% to 60% by weight relative to the total weight of the catalyst; the hydrogenation component comprises at least one hydrogenation metal present in a total amount ranging from 34% to 75% by weight calculated by the mass of oxides, relative to the total weight of the catalyst; and the hydrocracking catalyst has a specific surface area ranging from 150 m 2 /g to 350 m 2 /g and a pore volume ranging from 0.20 cm 3 /g to 0.50 cm 3 /g, such as from 0.30 cm 3 /g to 0.45 cm 3 /g, and the product (M×S) of the percentage amount of the total mass of the hydrogenation metal (M) and the specific surface area (S) is equal to or more than 100 m 2 /g, i.e., M×S≧100 m 2 /g. Also provided are the processes for preparing the hydrocracking catalysts and uses thereof.

1 . A hydrocracking catalyst comprising at least one cracking component and at least one hydrogenation component, wherein:
 the cracking component comprises at least one molecular sieve present in an amount ranging from 0% to 20% by weight relative to the total weight of the catalyst, and at least one amorphous silica-alumina present in an amount ranging from 20% to 60% by weight relative to the total weight of the catalyst;   the hydrogenation component comprises at least one hydrogenation metal present in a total amount ranging from 34% to 75% by weight calculated by the mass of oxides, relative to the total weight of the catalyst; and   the hydrocracking catalyst has a specific surface area ranging from 150 m 2 /g to 350 m 2 /g, a pore volume ranging from 0.20 cm 3 /g to 0.50 cm 3 /g, and the product (M×S) of the percentage amount of the total mass of the hydrogenation metal (M) and the specific surface area (S) is equal to or more than 100 m 2 /g.   
     
     
         2 . The catalyst according to  claim 1 , wherein the M×S ranges from 100 to 170 m 2 /g. 
     
     
         3 . The catalyst according to  claim 2 , wherein the M×S ranges from 120 to 160 m 2 /g. 
     
     
         4 . The catalyst according to  claim 1 , wherein the hydrogenation metal is in a total amount ranging from 40% to 60% by weight calculated by the oxide mass, relative to the total weight of the catalyst. 
     
     
         5 . The catalyst according to  claim 1 , wherein the hydrocracking catalyst has a specific surface area ranging from 160 m 2 /g to 300 m 2 /g, and a pore volume ranging from 0.30 cm 3 /g to 0.45 cm 3 /g. 
     
     
         6 . The catalyst according to  claim 1 , wherein the hydrocracking catalyst further comprises alumina, clay, and/or at least one auxiliary agent chosen from phosphorous, fluorine, boron, titanium, and zirconium. 
     
     
         7 . The catalyst according to  claim 1 , wherein the at least one molecular sieve is chosen from Y-type molecular sieves, β molecular sieves, ZSM-5 molecular sieves, SAPO molecular sieves, and MCM-41 mesoporous molecular sieves. 
     
     
         8 . The catalyst according to  claim 1 , wherein the at least one molecular sieve is present in an amount ranging from 1% to 10% by weight, relative to the total weight of the catalyst. 
     
     
         9 . The catalyst according to  claim 1 , wherein the at least one amorphous silica-alumina has a specific surface area ranging from 400 m 2 /g to 650 m 2 /g, a pore volume ranging from 1.0 cm 3 /g to 2.0 cm 3 /g, a silica amount ranging from 20% to 80% by weight relative to the total weight of the at least one amorphous silica-alumina, an average pore diameter ranging from 10 nm to 20 nm, and an infrared acid amount ranging from 0.3 mmol/g to 0.8 mmol/g. 
     
     
         10 . The catalyst according to  claim 1 , wherein the at least one amorphous silica-alumina has a specific surface area ranging from 400 to 550 m 2 /g, a pore volume ranging from 1.2 cm 3 /g to 1.6 cm 3 /g, a silica amount ranging from 30% to 65% by weight relative to the total weight of the at least one amorphous silica-alumina, and an average pore diameter ranging from 10 to 15 nm. 
     
     
         11 . The catalyst according to  claim 1 , wherein the at least one hydrogenation metal is chosen from W, Mo, Ni and Co. 
     
     
         12 . The catalyst according to  claim 11 , where in the at least one hydrogenation metal is chosen from W and Ni. 
     
     
         13 . The catalyst according to  claim 1 , prepared by the steps comprising
 (1) homogeneously mixing an optional molecular sieve powder with an amorphous silica-alumina precursor powder;   (2) formulating an impregnating solution comprising at least one hydrogenation active metal;   (3) impregnating the mixed powder in step (1) with the impregnating solution in step (2); and   (4) filtering, drying, pulverizing, adding an adhesive or a peptizing agent, molding, drying, and calcining to obtain a hydrocracking catalyst.   
     
     
         14 . The catalyst according to  claim 13 , wherein the amorphous silica-alumina precursor is an amorphous gelatinous silica-alumina dry powder prepared by the steps comprising:
 (1) conducting a neutralization and gelatinization reaction of an acidic aluminum salt solution with a mixed solution of alkaline sodium silicate and sodium aluminate at a temperature ranging from 20° C. to 80° C. and a pH value ranging from 4.0 to 9.5;   (2) adding at least one organosilicon source after gelatinization, wherein the at least one oragnosilicon source is chosen from organic silicon oils and silicon esters; the at least one organosilicon is added in an amount ranging from 5% to 40% relative to the total silicon amount present in the amorphous gelatinous silica-alumina dry powder, having an ageing temperature ranging from 60° C. to 80° C., a pH value ranging from 6.0 to 10.0, and an ageing time ranging from 60 minutes to 300 minutes;   (3) filtering and washing the sol obtained in step (2); and   (4) drying and pulverizing the filter cake obtained in step (3), to obtain the amorphous gelatinous silica-alumina dry powder.   
     
     
         15 . The catalyst according to  claim 1 , wherein the catalyst is used for the single-stage hydrocracking process. 
     
     
         16 . The process for preparing a hydrocracking catalyst, comprising the steps of
 (1) homogeneously mixing an amorphous silica-alumina precursor powder with an optional molecular sieve powder and an optional alumina powder;   (2) formulating an impregnating solution comprising at least one hydrogenation active metal component;   (3) impregnating the mixed powder in step (1) with the impregnating solution in step (2); and   (4) filtering, drying, pulverizing, adding an adhesive or a peptizing agent, molding, drying, and calcining to obtain the hydrocracking catalyst.   
     
     
         17 . The process according to  claim 16 , wherein the amorphous silica-alumina precursor is an amorphous gelatinous silica-alumina dry powder prepared by the steps comprising
 (1) conducting a neutralization and gelatinization reaction of an acidic aluminum salt solution with a mixed solution of alkaline sodium silicate and sodium aluminate at a temperature ranging from 20° C. to 80° C. and a pH value ranging from 4.0 to 9.5;   (2) adding at least one organosilicon source after gelatinization, wherein the at least one organosilicon source is chosen from organic silicon oils or silicon esters; the at least one organosilicon is added in an amount ranging from 5% to 40% relative to the total silicon amount present in the amorphous gelatinous silica-alumina dry powder, having an ageing temperature ranging from 60° C. to 80° C., a pH value ranging from 6.0 to 10.0, and an ageing time ranging from 60 minutes to 300 minutes;   (3) filtering and washing the sol obtained in step (2); and   (4) drying and pulverizing the filter cake obtained in step (3), to obtain the amorphous gelatinous silica-alumina dry powder.   
     
     
         18 . A single-stage hydrocracking process, wherein a vacuum gas oil is in contact with the hydrocracking catalyst according to  claim 1  in the presence of hydrogen gas. 
     
     
         19 . The single-stage hydrocracking process according to  claim 18 , wherein the hydrocracking reaction is conducted at a temperature ranging from 350° C. to 480° C. and a pressure ranging from 8 MPa to 20 MPa; with an vacuum gas oil having a liquid hourly volume space velocity ranging from 0.4 h −1  to 5 h −1 ; and with a volume ratio of hydrogen gas/vacuum gas oil under the standard state ranging from 100:1 to 3,000:1. 
     
     
         20 . The single-stage hydrocracking process according to  claim 18 , wherein, before and/or after the hydrocracking catalyst is employed, a hydrorefining catalyst is used in an amount ranging from 5% to 90% by volume relative to the volume of the hydrocracking catalyst. 
     
     
         21 . The single-stage hydrocracking process according to  claim 18 , wherein the hydrorefining catalyst is used in an amount ranging from 30% to 80% by volume relative to the volume of the hydrocracking catalyst. 
     
     
         22 . The single-stage hydrocracking process according to  claim 18 , wherein the vacuum gas oil has a final boiling point temperature ranging from 500° C. to 630° C.