Method of biomass conversion using a multifunctional catalyst system

Abstract

Solid biomass may be converted to hydrocarbons for use in renewable fuels uses by feeding biomass into a biomass conversion unit and pyrolyzing the biomass in the presence of a regenerated multi-functional catalyst. The regenerated multi-functional catalyst contains an acidic component, a basic component and a metallic component. The biomass is treated within the biomass conversion unit in at least two stages wherein at least one component of the regenerated multi-functional catalyst is fed into each of the stages.

What is claimed is: 
     
         1 . A process of converting solid biomass to hydrocarbons comprising feeding into a biomass conversion unit at least a portion of a regenerated catalyst in two stages wherein:
 (i) the regenerated catalyst comprises an acidic component, a basic component and a metallic component; and   (ii) treatment of the biomass within the biomass conversion unit occurs in at least two stages; and   (iii) at least one component of the regenerated catalyst is fed into each of the stages.   
     
     
         2 . The process of  claim 1 , wherein treatment of the biomass within the biomass conversion unit occurs in two stages. 
     
     
         3 . The process of  claim 2 , wherein at least a portion of the acidic component of the regenerated catalyst is fed into the biomass conversion unit during the first stage. 
     
     
         4 . The process of  claim 3 , wherein at least a portion of the basic component and the metallic component of the regenerated catalyst are fed into the biomass conversion unit during the second stage. 
     
     
         5 . The process of  claim 4 , wherein:
 a) fresh acidic component of the acidic component of the regenerated catalyst is further fed into the first stage;   b) fresh basic component and/or metallic component of the basic component and/or metallic component of the regenerated catalyst is further fed into the second stage; or   c) both (a) and (b).   
     
     
         6 . The process of  claim 1 , wherein at least one of the following conditions prevail:
 a) the acidic component is a mixture of zeolite ZSM-5 and zeolite USY;   b) the basic component is selected from the group consisting of alkaline-exchanged zeolite, alkaline earth-exchanged zeolite, basic zeolite, alkaline earth metal oxide, cerium oxide, zirconium oxide, titanium dioxide, mixed oxides of alkaline earth metal oxides and combinations thereof and mixed oxides selected from the group of magnesia-alumina, magnesia-silica, titania-alumina, titania-silica, ceria-alumina, ceria-silica, zirconia-alumina, zirconia-silica and mixtures thereof and wherein the exchanged zeolite has from about 40 to about 75% of exchanged cationic sites; or   c) the metallic component is selected from the group consisting of Cu, Ni, Cr, W, Mo, a metal carbide, a metal nitride, a metal sulfide and mixtures thereof.   
     
     
         7 . The process of  claim 1 , wherein the acidic component is a mixture of zeolite ZSM-5 and zeolite USY. 
     
     
         8 . The process of  claim 2 , wherein a promoter is further fed into the first stage or the second stage or both the first stage and the second stage. 
     
     
         9 . The process of  claim 8 , wherein at least one of the following conditions prevail:
 a) a phosphate promoter is further fed into the stage containing the acidic component of the catalyst;   b) a silica promoter, an alumina promoter or both a silica and alumina promoter are further fed into the stage containing the basic component of the catalyst; or   c) a metallic promoter is further fed into the stage containing the metallic component of the catalyst.   
     
     
         10 . The process of  claim 2 , wherein the basic component of the regenerated catalyst is fed into the biomass conversion unit during the first stage. 
     
     
         11 . The process of  claim 10 , wherein the acidic component and the metallic component of the regenerated catalyst are fed into the biomass conversion unit during the second stage. 
     
     
         12 . The process of  claim 11 , wherein:
 a) fresh basic component of the basic component of the regenerated catalyst is further fed into the first stage;   b) fresh acidic component and/or metallic component of the acidic component and/or metallic component of the regenerated catalyst is further fed into the second stage; or   c) both (a) and (b).   
     
     
         13 . The process of  claim 2 , wherein the metallic component of the regenerated catalyst is fed into the biomass conversion unit during the first stage. 
     
     
         14 . The process of  claim 13 , wherein the acidic component and the basic component of the regenerated catalyst are fed into the biomass conversion during the second stage. 
     
     
         15 . The process of  claim 14 , wherein:
 a) fresh metallic component of the metallic component of the regenerated catalyst is further fed into the first stage;   b) fresh acidic component and/or basic component of the acidic component and/or basic component of the regenerated catalyst is further fed into the second stage; or   c) both (a) and (b).   
     
     
         16 . The process of  claim 2 , wherein at least a portion of the acidic component and metallic component of the regenerated catalyst are fed into the biomass conversion unit during the first stage. 
     
     
         17 . The process of  claim 16 , wherein at least a portion of the basic component of the regenerated catalyst is fed into the biomass conversion unit during the second stage. 
     
     
         18 . The process of  claim 17 , wherein:
 a) fresh acidic component and/or metallic component of the acidic component and/or metallic component of the regenerated catalyst is further fed into the first stage;   b) fresh basic component of the basic component of the regenerated catalyst is further fed into the second stage; or   c) both (a) and (b).   
     
     
         19 . The process of  claim 2 , wherein at least a portion of the basic component and metallic component of the regenerated catalyst are fed into the biomass conversion unit during the first stage. 
     
     
         20 . The process of  claim 19 , wherein at least a portion of the acidic component of the regenerated catalyst is fed into the biomass conversion unit during the second stage. 
     
     
         21 . The process of  claim 20 , wherein:
 a) fresh basic component and/or metallic component of the basic and/or metallic component of the regenerated catalyst is further fed into the first stage;   b) fresh acidic component of the acidic component of the regenerated catalyst is further fed into the second stage; or   c) both (a) and (b).   
     
     
         22 . The process of  claim 2 , wherein at least a portion of the acidic component and basic component of the regenerated catalyst are fed into the biomass conversion unit during the first stage. 
     
     
         23 . The process of  claim 22 , wherein at least a portion of the metallic component of the regenerated catalyst is fed into the biomass conversion unit during the second stage. 
     
     
         24 . The process of  claim 23 , wherein:
 a) fresh acidic component and/or basic component of the acidic component and/or basic component of the regenerated catalyst is further fed into the first stage;   b) fresh metallic component of the metallic component of the regenerated catalyst is further fed into the second stage; or   c) both (a) and (b).   
     
     
         25 . A process of converting solid biomass to hydrocarbons in two stages in the presence of at least a portion of a first regenerated catalyst and at least a portion of a second regenerated catalyst wherein the first regenerated catalyst or the second regenerated catalyst is a monofunctional catalyst and the other is a bifunctional catalyst, wherein:
 (i) the combination of the monofunctional catalyst and the bifunctional catalyst contains an acidic component, a basic component and a metallic component wherein the bifunctional catalyst contains two of the components and the monofunctional catalyst contains the remaining component;   (ii) the first stage in a first reactor has a first solids separator and the second stage in a second reactor has a second solids separator; and   (iii) the first reactor has a first regeneration unit and the second reactor has a second regeneration unit   the process comprising:   a) subjecting the solid biomass to pyrolysis in the first reactor of the biomass conversion unit;   b) separating spent catalyst and vapor from the pyrolyzed biomass in the first solids separator;   c) feeding the separated vapor of step (b) into the second reactor and the spent catalyst into the first regeneration unit to render the first regenerated catalyst;   d) subjecting the vapor phase in the second reactor to pyrolysis;   e) feeding spent catalyst separated from the pyrolyzed vapor phase of step (d) into the second regeneration unit to render the second regenerated catalyst; and   f) feeding into the first reactor at least a portion of the first regenerated catalyst and feeding into the second reactor at least a portion of the second regenerated catalyst.   
     
     
         26 . The process of  claim 25 , wherein at least a portion of the monofunctional catalyst is fed into the first reactor. 
     
     
         27 . The process of  claim 26 , wherein the monofunctional catalyst contains the acidic component and the bifunctional catalyst contains the basic component and the metallic component. 
     
     
         28 . The process of  claim 27 , wherein:
 a) fresh acidic component of the acidic component of the monofunctional catalyst is further fed into the first reactor;   b) fresh basic component and/or metallic component of the basic component and/or metallic component of the bifunctional catalyst is further fed into the second reactor; or   c) both (a) and (b).   
     
     
         29 . The process of  claim 25 , wherein the first stage or the second stage or both the first stage and the second stage further comprises a promoter. 
     
     
         30 . The process of  claim 29 , wherein at least one of the following conditions prevail:
 a) the stage comprising the acidic component further comprises a phosphate promoter;   b) the basic component further comprises a silica promoter, an alumina promoter or both a silica promoter or an alumina promoter; or   c) the stage comprising the metallic component further comprises a metallic promoter.   
     
     
         31 . The process of  claim 25 , wherein at least a portion of the basic component of the regenerated catalyst is fed into the biomass conversion unit during the first stage. 
     
     
         32 . The process of  claim 31 , wherein at least a portion of the acidic component and the metallic component of the regenerated catalyst are fed into the second reactor. 
     
     
         33 . The process of  claim 32 , wherein:
 a) fresh basic component of the basic component of the regenerated catalyst is further fed into the first reactor;   b) fresh acidic component and/or metallic component of the acidic component and/or metallic component of the regenerated catalyst is further fed into the second reactor; or   c) both (a) and (b).   
     
     
         34 . The process of  claim 25 , wherein at least a portion of the metallic component of the regenerated catalyst is fed into the first reactor. 
     
     
         35 . The process of  claim 34 , wherein at least a portion of the acidic component and the basic component of the regenerated catalyst are fed into the second reactor. 
     
     
         36 . The process of  claim 35 , wherein:
 a) fresh metallic component of the metallic component of the regenerated catalyst is further fed into the first reactor;   b) fresh acidic component and/or basic component of the acidic component and/or basic component of the regenerated catalyst is further fed into the second reactor; or   c) both (a) and (b).   
     
     
         37 . The process of  claim 25 , wherein at least a portion of the bi-functional catalyst is fed into the first reactor. 
     
     
         38 . The process of  claim 37 , wherein at least a portion of the acidic component and metallic component of the regenerated catalyst are fed into the first reactor. 
     
     
         39 . The process of  claim 38 , wherein at least a portion of the basic component of the regenerated catalyst is fed into the second reactor. 
     
     
         40 . The process of  claim 39 , wherein:
 a) fresh acidic component and/or metallic component of the acidic component and/or metallic component of the regenerated catalyst is further fed into the first reactor;   b) fresh basic component of the basic component of the regenerated catalyst is further fed into the second stage; or   c) both (a) and (b).   
     
     
         41 . The process of  claim 37 , wherein at least a portion of the basic component and metallic component of the regenerated catalyst are fed into the first reactor. 
     
     
         42 . The process of  claim 41 , wherein at least a portion of the acidic component of the regenerated catalyst is fed into the second reactor. 
     
     
         43 . The process of  claim 42 , wherein:
 a) fresh basic component and/or fresh metallic component of the basic component and/or metallic component of the regenerated catalyst is further fed into the first reactor;   b) fresh acidic component of the acidic component of the regenerated catalyst is further fed into the second reactor; or   c) both (a) and (b).   
     
     
         44 . The process of  claim 37 , wherein at least a portion of the acidic component and basic component of the regenerated catalyst are fed into the first reactor. 
     
     
         45 . The process of  claim 44 , wherein at least a portion of the metallic component of the regenerated catalyst is fed into the second reactor. 
     
     
         46 . The process of  claim 45 , wherein:
 a) fresh acidic component and/or fresh basic component of the acidic component and/or basic component of the regenerated catalyst is further fed into the first stage;   b) fresh metallic component of the metallic component of the regenerated catalyst is further fed into the second stage; or   c) both (a) and (b).   
     
     
         47 . A process of converting solid biomass to hydrocarbons in at least two stages within a biomass conversion unit wherein at least one of the stages is conducted in the presence of at least a portion of a regenerated multi-functional catalyst comprising an acid component, a basic component and a metallic material, the process comprising:
 a) pyrolyzing the biomass in a first stage in a first reactor in the absence of a catalyst in a first stage; and   b) separating vapor and solids from the pyrolyzed biomass;   c) feeding the separated vapor into a second stage in a second reactor; and   d) converting the separated vapor into hydrocarbons in the presence of the regenerated catalyst in a conversion unit.   
     
     
         48 . The process of  claim 47 , wherein at least one of the following conditions prevail:
 a) the acidic component of the regenerated catalyst is a mixture of zeolite ZSM-5 and zeolite USY;   b) the basic component of the regenerated catalyst is selected from the group consisting of alkaline-exchanged zeolite, alkaline earth-exchanged zeolite, basic zeolite, alkaline earth metal oxide, cerium oxide, zirconium oxide, titanium dioxide, mixed oxides of alkaline earth metal oxides and combinations thereof and mixed oxides selected from the group of magnesia-alumina, magnesia-silica, titania-alumina, titania-silica, ceria-alumina, ceria-silica, zirconia-alumina, zirconia-silica and mixtures thereof and wherein the exchanged zeolite has from about 40 to about 75% of exchanged cationic sites; or   c) the metallic component is selected from the group consisting of Cu, Ni, Cr, W, Mo, a metal carbide, a metal nitride, a metal sulfide and mixtures thereof.   
     
     
         49 . A process of converting solid biomass to hydrocarbons in at least two stages comprising:
 a) pyrolyzing the biomass in a first stage in a first reactor in the absence of a catalyst;   b) separating solids and vapor from the pyrolyzed product of step (a);   c) feeding into a second stage in a second reactor at least a portion of a regenerated catalyst comprising an acidic component, a basic component and a metallic component; and   d) pyrolyzing vapor separated in step (b) in the presence of at least a portion of the regenerated catalyst.   
     
     
         50 . The process of  claim 49 , wherein one or more components of the regenerated catalyst are fed into the second reactor and the remaining component(s) are fed into a third reactor. 
     
     
         51 . The process of  claim 49 , wherein at least one of the following conditions prevail:
 a) the acidic component is a mixture of zeolite ZSM-5 and zeolite USY;   b) the basic component of the regenerated catalyst is selected from the group consisting of alkaline-exchanged zeolite, alkaline earth-exchanged zeolite, basic zeolite, alkaline earth metal oxide, cerium oxide, zirconium oxide, titanium dioxide, mixed oxides of alkaline earth metal oxides and combinations thereof and mixed oxides selected from the group of magnesia-alumina, magnesia-silica, titania-alumina, titania-silica, ceria-alumina, ceria-silica, zirconia-alumina, zirconia-silica and mixtures thereof and wherein the exchanged zeolite has from about 40 to about 75% of exchanged cationic sites; or   c) the metallic component is selected from the group consisting of Cu, Ni, Cr, W, Mo, a metal carbide, a metal nitride, a metal sulfide and mixtures thereof.   
     
     
         52 . The process of  claim 50 , wherein at least a portion of the acidic component of the regenerated catalyst is fed into the second reactor and at least a portion of the basic component and the metallic component of the regenerated catalyst are fed into the third reactor. 
     
     
         53 . The process of  claim 50 , wherein at least a portion of the basic component of the regenerated catalyst is fed into the second reactor and at least a portion of the acidic component and the metallic component of the regenerated catalyst are fed into the third reactor. 
     
     
         54 . The process of  claim 50 , wherein at least a portion of the metallic component of the regenerated catalyst is fed into the second reactor and at least a portion of the acidic component and the basic component of the regenerated catalyst are fed into the biomass-vapors staged-conversion into the third reactor. 
     
     
         55 . The process of  claim 50 , wherein at least a portion of the acidic component and metallic component of the regenerated catalyst are fed into the second reactor and at least a portion of the basic component of the regenerated catalyst is fed into the third reactor. 
     
     
         56 . The process of  claim 50 , wherein at least a portion of the basic and metallic component of the regenerated catalyst are fed into the second reactor and at least a portion of the acidic component of the regenerated catalyst is fed into the third reactor. 
     
     
         57 . The process of  claim 50 , wherein at least a portion of the acidic component and basic component are fed into the second reactor and the metallic component of the regenerated catalyst is fed into the third reactor. 
     
     
         58 . A process of converting solid biomass to hydrocarbons comprising the step of feeding into a biomass conversion unit at least a portion of a regenerated multi-functional catalyst comprising an acidic component, a basic component and a metallic component and pyrolyzing the biomass in the biomass conversion unit wherein at least one of the following conditions prevail:
 a) the regenerated multi-functional catalyst further comprises a binder;   b) the acidic component is the combination of zeolite ZSM-5 and zeolite USY;   c) the metallic component is selected from the group consisting of Cu, Ni, Cr, W, Mo, a metal carbide, a metal sulfide and mixtures thereof;   d) the basic material is selected from the group consisting of alkaline-exchanged zeolite, alkaline earth-exchanged zeolite, basic zeolite, alkaline earth metal oxide, cerium oxide, zirconium oxide, titanium dioxide, mixed oxides of alkaline earth metal oxides and combinations thereof and mixed oxides selected from the group of magnesia-alumina, magnesia-silica, titania-alumina, titania-silica, ceria-alumina, ceria-silica, zirconia-alumina, zirconia-silica and mixtures thereof and wherein the exchanged zeolite has from about 40 to about 75% of exchanged cationic sites; or   e) the multi-functional catalyst further contains at least one promoter.