Methods of hydrocracking hydrocarbon oils

Abstract

A method of hydrocracking a hydrocarbon oil may comprise contacting the hydrocarbon oil with a catalyst suitable for hydrocracking in the presence of hydrogen in a reactor, wherein the catalyst comprises from 19.9 wt. % to 97.9 wt. % of a support material; from 2 wt. % to 80 wt. % of a zeolitic material comprising a microporous framework comprising zirconium oxide, titanium oxide, or both; and from 0.1 wt. % to 40 wt. % of one or more metals, one or more metal oxides, or both. The one or more metals, the one or more metal oxides, or both, may be disposed on the microporous framework, the support material, or both. When the catalyst is utilized in a hydrocracking reaction to crack vacuum gas oil, the activation energy of the hydrocracking reaction may be less than or equal to 55 Kcal/mol.

What is claimed is: 
     
         1 . A method of hydrocracking a hydrocarbon oil, the method comprising:
 contacting the hydrocarbon oil with a catalyst suitable for hydrocracking in the presence of hydrogen in a reactor, wherein:   the catalyst comprises:
 from 19.9 wt. % to 97.9 wt. % of a support material; 
 from 2 wt. % to 80 wt. % of a zeolitic material comprising a microporous framework comprising zirconium oxide, titanium oxide, or both; and 
 from 0.1 wt. % to 40 wt. % of one or more metals, one or more metal oxides, or both, wherein the one or more metals are chosen from cobalt atoms, molybdenum atoms, nickel atoms, tungsten atoms, or combinations thereof, wherein the one or more metal oxides are chosen from cobalt oxide, molybdenum oxide, nickel oxide, tungsten oxide, or combinations thereof, and wherein the one or more metals, the one or more metal oxides, or both, are disposed on the microporous framework, the support material, or both; and 
   wherein when the catalyst is utilized in a hydrocracking reaction to crack vacuum gas oil, the activation energy of the hydrocracking reaction is less than or equal to 55 Kcal/mol, wherein the vacuum gas oil has an initial boiling point of from 205° C. to 225° C. and a 95 wt. % point of from 555° C. to 575° C., and the ratio of hydrogen to the vacuum gas oil is 1,000 StL/L.   
     
     
         2 . The method of  claim 1 , wherein the hydrocarbon oil is a vacuum gas oil having an initial boiling point of greater than or equal to 200° C. and less than or equal to 375° C. and a 95 wt. % boiling point of greater than or equal to 500° C. and less than or equal to 650° C. 
     
     
         3 . The method of  claim 1 , wherein less than 5 wt. % of the hydrocarbon oil has a boiling point of less than or equal to 300° C. 
     
     
         4 . The method of  claim 1 , wherein greater than 50 wt. % of the hydrocarbon oil has a boiling point of greater than or equal to 400° C. 
     
     
         5 . The method of  claim 1 , wherein the contacting causes at least a portion of hydrocarbons in the hydrocarbon oil to undergo cracking reactions to produce a cracked effluent having a boiling point from 32° C. to 145° C. 
     
     
         6 . The method of  claim 1 , wherein at least 6 wt. % of the cracked effluent has a boiling point from 32° C. to 145° C. 
     
     
         7 . The method of  claim 1 , wherein a temperature of the reactor during the contacting is from 300° C. to 500° C. 
     
     
         8 . The method of  claim 1 , wherein a volumetric ratio of the hydrogen to the hydrocarbon oil during the contacting is from 500 Nm 3 /m 3  to 2,500 Nm 3 /m 3 . 
     
     
         9 . The method of  claim 1 , wherein the reactor has a hydrogen pressure from 40 kg/cm 2  to 300 kg/cm 2  during the contacting. 
     
     
         10 . The method of  claim 1 , wherein the zeolitic material comprises from 0.1 wt. % to 5 wt. % of the zirconium oxide. 
     
     
         11 . The method of  claim 1 , wherein the zeolitic material comprises from 0.1 wt. % to 5 wt. % of the titanium oxide. 
     
     
         12 . The method of  claim 1 , wherein the zeolitic material comprises from 0.1 wt. % to 5 wt. % of the zirconium oxide, and from 0.1 wt. % to 5 wt. % of the titanium oxide. 
     
     
         13 . The method of  claim 1 , wherein the zeolitic material comprises an ultra-stable zeolite Y. 
     
     
         14 . The method of  claim 1 , wherein the zeolitic material has a crystal lattice constant of from 2.430 nm to 2.450 nm. 
     
     
         15 . The method of  claim 1 , wherein the zeolitic material has a specific surface area of 600 m 2 /g to 900 m 2 /g. 
     
     
         16 . The method of  claim 1 , wherein the support material comprises an inorganic oxide excluding the zeolitic material. 
     
     
         17 . The method of  claim 1 , wherein the catalyst has a volume of pores having a diameter of less than or equal to 600 Å from 0.40 mL/g to 0.75 mL/g. 
     
     
         18 . The method of  claim 1 , further comprising making the catalyst, wherein making the catalyst comprises:
 contacting an initial catalyst with a passivation agent to form a passivated catalyst, wherein the initial catalyst comprises acid sites, and wherein the passivation agent binds to a portion or all of the acid sites on the initial catalyst;   contacting the passivated catalyst with a metal precursor to form a doped catalyst, wherein the metal precursor comprises one or more metals, one or more metal salts, or both, the one or more metals, one or more metal salts, or combinations thereof comprising cobalt atoms, molybdenum atoms, nickel atoms, tungsten atoms, or combinations thereof; and   heating the doped catalyst to form the catalyst suitable for hydrocracking.   
     
     
         19 . The method of  claim 1 , wherein the catalyst is made by a method comprising:
 contacting an initial catalyst with a passivation agent to form a passivated catalyst, wherein the initial catalyst comprises acid sites, and wherein the passivation agent binds to a portion or all of the acid sites on the initial catalyst;   contacting the passivated catalyst with a metal precursor to form a doped catalyst, wherein the metal precursor comprises one or more metals, one or more metal salts, or both, the one or more metals, one or more metal salts, or combinations thereof comprising cobalt atoms, molybdenum atoms, nickel atoms, tungsten atoms, or combinations thereof; and   heating the doped catalyst to form the catalyst suitable for hydrocracking.   
     
     
         20 . The method of  claim 19 , wherein the passivation agent comprises ammonia.