Hydrogenation of solid carbonaceous materials using mixed catalysts

Abstract

This invention encompasses systems and methods for converting solid carbonaceous material to a liquid product, comprising maintaining a solid carbonaceous material in the presence of at least one active source of titanium and at least one active source of a second metal at a reaction temperature of greater than 350° C. and at a pressure in the range of 300 to 5000 psig for a time sufficient to form a liquid product.

1 . A process for converting solid carbonaceous material to a liquid product, comprising maintaining a solid carbonaceous material in the presence of at least one active source of titanium and at least one active source of a second metal at a reaction temperature of greater than 350° C. and at a pressure in the range of 300 to 5000 psig for a time sufficient to form a liquid product. 
     
     
         2 . The process of  claim 1 , the process comprising:
 a) preparing a combination of the solid carbonaceous material, at least one hydrocarbonaceous liquid, at least one active source of titanium and at least one active source of the second metal; and   b) passing the combination to a hydroconversion reaction zone and maintaining the solid carbonaceous material at a reaction temperature of greater than 350° C. and at a pressure in the range of 300 to 5000 psig for a time sufficient to convert at least a portion of the solid carbonaceous material to a liquid product boiling in the temperature range of C 5  to 650° C.   
     
     
         3 . The process of  claim 2 , wherein the step of preparing the combination comprises:
 a) preparing a mixture comprising at least one active source of titanium and at least one active source of a second metal;   b) combining the mixture with coal to form catalyst-containing coal particles; and   c) providing a hydrocarbonaceous liquid to the catalyst-containing coal particles to prepare the combination.   
     
     
         4 . The process of  claim 3 , further comprising drying the catalyst-containing coal particles prior to the step of passing the combination to the hydroconversion reaction zone. 
     
     
         5 . The process of  claim 3 , wherein the mixture further comprises a surfactant. 
     
     
         6 . The process of  claim 2 , further supplying an active source of sulfur to the combination. 
     
     
         7 . The process of  claim 6 , wherein the active source of sulfur is supplied at an atomic ratio of sulfur to metal within the range of between 0.1 to 1 and 10 to 1. 
     
     
         8 . The process of  claim 2 , further comprising supplying hydrogen or hydrogen-containing gas to the hydroconversion reaction zone. 
     
     
         9 . The process of  claim 2 , further comprising pretreating the combination at a pretreatment temperature within the range of 100-350° C. and for a time of between 5 and 600 minutes prior to passing the combination to the hydroconversion reaction zone. 
     
     
         10 . The process of  claim 9 , further comprising pretreating the combination in the presence of an active source of sulfur. 
     
     
         11 . The process of  claim 9 , further comprising pretreating the combination in the presence of hydrogen or a hydrogen-containing gas. 
     
     
         12 . The process of  claim 1 , wherein the second metal is selected from the group consisting of iron, molybdenum, nickel, manganese, vanadium, tungsten, cobalt, copper, chromium, zinc and tin. 
     
     
         13 . The process of  claim 1 , wherein the second metal is iron. 
     
     
         14 . The process of  claim 1 , wherein the titanium is present in an amount of 10 ppm to 10 wt %, based on dry, ash free coal. 
     
     
         15 . The process of  claim 1 , wherein the second metal is present in an amount of 10 ppm to 10 wt %, based on dry, ash free coal. 
     
     
         16 . The process of  claim 1 , wherein titanium and the second metal are present in a molar ratio within the range of between 0.1 to 1 and 10 to 1. 
     
     
         17 . The process of  claim 1  further comprising maintaining the solid carbonaceous material in the presence of at least one active source of sulfur. 
     
     
         18 . The process of  claim 1 , further comprising maintaining the solid carbonaceous material in the presence of hydrogen or a hydrogen containing gas. 
     
     
         19 . The process of  claim 2 , further comprising converting at least 25% by weight of the solid carbonaceous material to a liquid product boiling in the temperature range of C 5  to 650° C. 
     
     
         20 . The process of  claim 19 , further comprising converting in the range 30% to 99% by weight of the solid carbonaceous material to the liquid product. 
     
     
         21 . The process of  claim 2 , further comprising maintaining the solid carbonaceous material at a reaction temperature in the range of between 350° C. and 800° C. 
     
     
         22 . The process of  claim 1 , wherein the active source of titanium and the active source of the second metal form a catalyst composition having a formula:
   (R p ) i (M t ) a (L u ) b (S v ) d (C w ) e (H x ) f (O y ) g (N z ) h ,   
       wherein
 R is optional, R is at least a lanthanoid element metal or an alkaline earth metal; 
 M is titanium; 
 L is at least a “d” block element metal different from the “d” block element metal M;
   0<=i<=1; 
   0 <b/a=< 5, 
   0.5( a+b )<= d<= 5( a+b ), 
   0< e<= 11( a+b ), 
   0 <f<= 7( a+b ), 
   0< g<= 5( a+b ), 
   0< h<= 2( a+b ), 
 
 p, t, u, v, w, x, y, z, each representing total charge for each of: M, L, S, C, H, O and N, respectively, wherein pi+ta+ub+vd+we+xf+yg+zh=0, S=sulfur, C=carbon, H=hydrogen, O=oxygen and N=nitrogen. 
 
     
     
         23 . The process of  claim 22 , wherein L is selected from the group consisting of iron, molybdenum, manganese, vanadium, tungsten, cobalt, copper, nickel, chromium, platinum, palladium, cerium, zirconium, zinc and tin. 
     
     
         24 . The process of  claim 23 , wherein L is iron.