Hydrocracking catalyst and method of hydrocracking heavy oil

Abstract

In a process of hydrocracking heavy oil with a catalyst in petroleum refining, asphaltene contained in heavy oil, and impurities including heavy metals such as nickel and vanadium, are efficiently removed with activated carbon, whereby the reduction in catalyst activity or formation of coke by the impurities can be prevented. The invention provides a hydrocracking catalyst comprising activated carbon extrudate as a carrier activated with steam and having a high distribution of pores having pore sizes in the range of 20 to 200 nm.

1 . A method of hydrocracking heavy oil, comprising the step of hydrocracking heavy oil in a fixed bed, a moving bed or an ebullating bed with a hydrocracking catalyst comprising activated carbon extrudate as a carrier activated with steam and having a high distribution of pores having pore diameter in the range of 20 to 200 nm and any one of the group VIIIB metals selected from iron, nickel and cobalt or molybdenum, both nickel and molybdenum, or both cobalt and molybdenum, under the conditions of a pressure of 8 to 20 MPa, a temperature of 380 to 450° C., an LHSV of 0.1 to 1.0 hr −1 , and an H 2 /oil ratio of 350 to 1500 Nm 3 /kl-oil.  
     
     
         2 . The method according to  claim 1 , wherein the heavy oil is a hydrocarbon oil containing 70 vol % fraction or more with the boiling point at 525° C. or more, a hydrocarbon oil containing at least 200 to 2000 wppm nickel and/or vanadium as heavy metal, or a hydrocarbon oil containing 8 to 30 wt % asphaltene (heptane insolubles).  
     
     
         3 . The method according to  claim 1 , wherein, in the activated carbon extrudate, the volume of pores determined by mercury porosimetry is 0.7 to 1.8 ml/g, the proportion of pores having pore diameter in the range of 20 to 200 nm is 20 vol % or more, and the ratio by volume of pores having pore diameter in the range of 38 to 90 nm to pores having pore diameter in the range of 20 to 200 nm is 40% or more.  
     
     
         4 . The method according to  claim 1 , wherein, in the activated carbon extrudate, the volume of pores determined by mercury porosimetry is 0.7 to 1.8 ml/g, the proportion of pores having pore diameter in the range of 20 to 200 nm is 20 vol % or more, the ratio by volume of pores having pore diameter in the range of 38 to 90 nm to pores having pore diameter in the range of 20 to 200 nm is 40% or more, and the ability of the activated carbon to adsorb asphaltene is 22%/ml or more.  
     
     
         5 . The method according to  claim 1 , wherein the catalyst comprises iron, cobalt or nickel as the catalyst component.  
     
     
         6 . A hydrocracking catalyst comprising activated carbon extrudate as a carrier activated with steam and having a high distribution of pores having pore diameter in the range of 20 to 200 nm and any one of the group VIIIB metals selected from iron, nickel and cobalt or molybdenum, both nickel and molybdenum, or both cobalt and molybdenum.  
     
     
         7 . The catalyst according to  claim 6 , wherein, in the activated carbon extrudate, the volume of pores determined by mercury porosimetry is 0.7 to 1.8 ml/g, the proportion of pores having pore diameter in the range of 20 to 200 nm is 20 vol % or more, and the ratio by volume of pores having pore diameter in the range of 38 to 90 nm to pores having pore diameter in the range of 20 to 200 nm is 40% or more.  
     
     
         8 . The catalyst according to  claim 6 , wherein, in the activated carbon extrudate, the volume of pores determined by mercury porosimetry is 0.7 to 1.8 ml/g, the proportion of pores having pore diameter in the range of 20 to 200 nm is 20 vol % or more, the ratio by volume of pores having pore diameter in the range of 38 to 90 nm to pores having pore diameter in the range of 20 to 200 nm is 40% or more, and the ability of the activated carbon to adsorb asphaltene is 22%/ml or more.  
     
     
         9 . A hydrocracking catalyst, comprising activated carbon extrudate as a carrier, activated with steam, and having a pore size distribution with a high proportion of pores having pore diameter in the range of 20 to 200 nm, the pore size distribution particularly having a peak; and any one of the group VIII metals selected from iron, nickel, and cobalt, or molybdenum; both nickel and molybdenum; or both cobalt and molybdenum.  
     
     
         10 . The catalyst according to  claim 9 , wherein the volume proportion of pores in the range of 20 to 200 nm is 20% or more; the volume ration of pores having a pore diameter in the range of 38 to 90 nm to pores having a pore diameter in the range of 20 to 200 nm is more than 40%; and/or the differential pore size distribution has a peak, said peak being in the pore size range 20 to 200 nm, or/and said peak having a height of at least 0.4 cm 3 /g.  
     
     
         11 . A process of manufacturing a hydrocracking catalyst, comprising the steps of providing a starting carbon source, grinding said starting carbon source into fine particles; preparing an extrudable mixture from said fine particles; molding the material by extruding; activating the extrudate with an activating gas; and converting the activated carbon extrudate into the catalyst by adding a catalyzing metal or metal compound; characterized in that said activating gas comprises steam and optionally air, such that the oxygen content is not more than 4 vol %.  
     
     
         12 . The process according to  claim 11 , in which the starting carbon source is selected from the group consisting of charcoal, coconut shell carbon, peat, lignite, brown coal, bituminous coal and petroleum cokes; the material is extruded at a pressure of 300 to 600 Mpa; and the extrudate is activated with an activating gas for 4 to 12 hours.  
     
     
         13 . The process according to  claim 11 , which further comprises providing an activated carbon extrudate and again activating said activated carbon extrudate with steam.  
     
     
         14 . The catalyst, obtainable by the process according to  claim 11 .  
     
     
         15 . Use of the catalyst according to  claim 6  for hydrocracking a heavy oil.  
     
     
         16 . The method according to  claim 1 , wherein the catalyst is obtainable by a process comprising the steps of providing a starting carbon source, grinding said starting carbon source into fine particles; preparing an extrudable mixture from said fine particles; molding the material by extruding; activating the extrudate with an activating gas; and converting the activated carbon extrudate into the catalyst by adding a catalyzing metal or metal compound; characterized in that said activating gas comprises steam and optionally air, such that the oxygen content is not more than 4 vol %.