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This invention relates to compositions and methods for fluid hydrocarbon product, and more specifically, to compositions and methods for fluid hydrocarbon product via catalytic pyrolysis. Some embodiments relate to methods for the production of specific aromatic products (e.g., benzene, toluene, nap

This invention relates to compositions and methods for fluid hydrocarbon product, and more specifically, to compositions and methods for fluid hydrocarbon product via catalytic pyrolysis. Some embodiments relate to methods for the production of specific aromatic products (e.g., benzene, toluene, naphthalene, xylene, etc.) via catalytic pyrolysis. Some such methods may involve the use of a composition comprising a mixture of a solid hydrocarbonaceous material and a heterogeneous pyrolytic catalyst component. In some embodiments, an olefin compound may be co-fed to the reactor and/or separated from a product stream and recycled to the reactor to improve yield and/or selectivity of certain products. The methods described herein may also involve the use of specialized catalysts. For example, in some cases, zeolite catalysts may be used. In some instances, the catalysts are characterized by particle sizes in certain identified ranges that can lead to improve yield and/or selectivity of certain products.

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1. A method for producing one or more fluid hydrocarbon products from a solid hydrocarbonaceous material comprising: feeding the solid hydrocarbonaceous material to a reactor, wherein the solid hydrocarbonaceous material comprises lignocellulosic biomass;pyrolyzing within the reactor at least a port

1. A method for producing one or more fluid hydrocarbon products from a solid hydrocarbonaceous material comprising: feeding the solid hydrocarbonaceous material to a reactor, wherein the solid hydrocarbonaceous material comprises lignocellulosic biomass;pyrolyzing within the reactor at least a portion of the solid hydrocarbonaceous material under reaction conditions sufficient to produce one or more pyrolysis products;reacting within the reactor in the presence of a catalyst at least a portion of the one or more pyrolysis products under reaction conditions sufficient to produce the one or more fluid hydrocarbon products, wherein the one or more fluid hydrocarbon products comprise olefins and aromatics, and wherein the catalyst comprises particles having a pore size of less than about 100 Angstroms;flowing the one or more fluid hydrocarbon products out of the reactor;separating at least a portion of the olefins from the one or more fluid hydrocarbon products to produce a recycle stream comprising the separated olefins and a product stream comprising a remainder of the one or more fluid hydrocarbon products;recovering said product stream; andrecycling at least a portion of the recycle stream to the reactor to increase the amount of aromatic compounds in the one or more fluid hydrocarbon products; wherein the ratio of the mass of carbon within the solid hydrocarbonaceous material fed to the reactor to the mass of carbon in the olefins in the recycle stream is at least about 2:1, the aromatics in the one or more fluid hydrocarbon products comprise benzene, toluene, xylene, naphthalene or a mixture of two or more thereof, an amount of benzene, toluene, xylene, naphthalene or a mixture of two or more thereof in the one or more fluid hydrocarbon products is at least about 10% by weight based on the weight of the hydrocarbonaceous material used in forming the one or more pyrolysis products. 2. A method as in claim 1, wherein: the catalyst comprises silica and alumina and pores with a pore size in the range from about 5 to about 100 Angstroms. 3. A method as in claim 1, wherein the ratio of the mass of carbon within the solid hydrocarbonaceous material to the mass of carbon in the olefins in the recycle stream is between about 2:1 and about 20:1. 4. A method as in claim 1, wherein the ratio of the mass of carbon within the solid hydrocarbonaceous material to the mass of carbon in the olefins in the recycle stream is between about 3:1 and about 10:1. 5. A method as in claim 1, wherein the ratio of the mass of carbon within the solid hydrocarbonaceous material to the mass of carbon in the olefins in the recycle stream is between about 4:1 and about 5:1. 6. A method as in claim 1, wherein the reactor is a fluidized bed reactor. 7. A method as in claim 1, wherein the reactor is a circulating fluidized bed reactor or a turbulent fluidized bed reactor. 8. A method as in claim 1, wherein the solid hydrocarbonaceous material is fed to the reactor at a mass-normalized space velocity of between about 0.01 hour−1 and about 10 hour−1. 9. A method as in claim 8, further comprising varying the mass-normalized space velocity of the solid hydrocarbonaceous material to selectively produce different fluid hydrocarbon products. 10. A method as in claim 1, wherein the solid hydrocarbonaceous material comprises sugar cane bagasse, glucose, wood, corn stover, or a combination of two or more thereof. 11. A method as in claim 6, further comprising introducing a fluidization fluid into the fluidized bed reactor, the fluidization fluid having an average fluidization fluid residence time of at least about 10 seconds in the reactor. 12. A method as in claim 1, wherein the temperature in the reactor is between about 500° C. and about 1000° C. 13. A method as in claim 1, wherein the temperature in the reactor is at least about 700° C. 14. A method as in claim 1, wherein the one or more fluid hydrocarbon products comprise an amount of benzene, toluene, xylene, naphthalene, or a mixture of two or more thereof that is at least 15 wt % of the one or more fluid hydrocarbon products. 15. A method as in claim 1, wherein the reactor has a volume of at least about 1 liter. 16. A method as in claim 1, wherein the solid hydrocarbonaceous material and the catalyst are fed in one or more feed streams to the reactor such that the mass ratio of the catalyst to the solid hydrocarbonaceous material in the one or more feed streams is from about 0.5:1 to about 20:1. 17. A method as in claim 1, wherein a residence time of the solid hydrocarbonaceous material in the reactor is at least about 10 seconds. 18. A method as in claim 1, wherein the solid hydrocarbonaceous material comprises a first component and a second component, wherein the first and second components are different; and further comprising: providing a first and a second catalyst to the reactor, wherein the first catalyst is selective for catalytically reacting the first component or a derivative thereof to produce a fluid hydrocarbon product, and the second catalyst is selective for catalytically reacting the second component or a derivative thereof to produce a fluid hydrocarbon product. 19. A method as in claim 1, wherein the contents of the reactor in which the pyrolyzing step occurs are heated at a heating rate of greater than about 50° C./s. 20. A method as in claim 1, wherein the contents of the reactor in which the catalytic reaction step occurs are heated at a heating rate of greater than about 50° C./s. 21. A method as in claim 1, wherein the one or more fluid hydrocarbon products are produced from the pyrolysis products by dehydration, decarbonylation, decarboxylation, isomerization, oligomerization and/or dehydrogenation catalytic reactions. 22. The method of claim 1 wherein the catalyst comprises silica and alumina, in a silica to alumina molar ratio of at least about 30:1. 23. The method of claim 1 wherein the catalyst comprises silica and alumina, in a silica to alumina molar ratio of at least about 150:1. 24. The method of claim 1 wherein the catalyst comprises silica and alumina, in a silica to alumina molar ratio in the range from about 30:1 to about 200:1. 25. A method as in claim 1, wherein the catalyst comprises one or more of a zeolite catalyst, a non-zeolite catalyst, a metal catalyst and/or a metal oxide catalyst. 26. A method as in claim 1, wherein the catalyst comprises a zeolite catalyst. 27. A method as in claim 1, wherein the catalyst comprises ZSM-5. 28. A method as in claim 1, wherein the catalyst comprises silica and alumina in a silica to alumina molar ratio of from about 30:1 to about 200:1. 29. A method for producing one or more fluid hydrocarbon products from a solid hydrocarbonaceous material comprising: feeding the solid hydrocarbonaceous material to a fluidized bed reactor and contacting a catalyst with the solid hydrocarbonaceous material in the reactor, wherein the solid hydrocarbonaceous material comprises lignocellulosic biomass, the catalyst particles having a pore size of less than about 100 Angstroms, the catalyst comprises silica and alumina in a silica to alumina molar ratio of at least about 30:1;pyrolyzing within the reactor at least a portion of the solid hydrocarbonaceous material under reaction conditions sufficient to produce one or more pyrolysis products;catalytically reacting within the reactor at least a portion of the one or more pyrolysis products under reaction conditions sufficient to produce the one or more fluid hydrocarbon products, wherein the one or more fluid hydrocarbon products comprise olefins and aromatics;flowing a product stream comprising the one or more fluid hydrocarbon products out of the reactor;separating at least a portion of the olefins from the one or more fluid hydrocarbon products to produce a recycle stream comprising the separated olefins and a product stream comprising a remainder of the one or more fluid hydrocarbon products;recovering said product stream; andrecycling at least a portion of the recycle stream to the reactor to increase the amount of aromatic compounds in the one or more fluid hydrocarbon products; wherein the ratio of the mass of carbon within the solid hydrocarbonaceous material fed to the reactor to the mass of carbon in the olefins in the recycle stream is from about 2:1 to about 20:1[N], the aromatics in the one or more fluid hydrocarbon products comprise benzene, toluene, xylene, naphthalene or a mixture of two or more thereof, an amount of benzene, toluene, xylene, naphthalene or a mixture of two or more thereof in the one or more fluid hydrocarbon is at least about 15% by weight based on the weight of the hydrocarbonaceous material used in forming the one or more pyrolysis products; andwherein a residence time of the solid hydrocarbonaceous material in the reactor is at least about 10 seconds, the residence time being calculated by dividing the volume of the reactor with the volumetric flow rate of hydrocarbonaceous material and the one or more fluid hydrocarbon products exiting the reactor. 30. A method as in claim 29, wherein the silica to alumina molar ratio is at least about 50:1. 31. A method as in claim 29, wherein the silica to alumina molar ratio is at least about 150:1. 32. A method as in claim 29, wherein the silica to alumina molar ratio is in the range from about 30:1 to about 150:1. 33. A method as in claim 29 wherein the catalyst comprises a zeolite catalyst having a bimodal distribution of pore sizes. 34. A method as in claim 29, wherein the catalyst comprises a plurality of pores; at least about 95% of the pores of the one or more catalysts have smallest cross-sectional diameters that lie within a first size distribution or a second size distribution;at least about 5% of the pores of the one or more catalysts have smallest cross-sectional diameters that lie within the first size distribution;at least about 5% of the pores of the one or more catalysts have smallest cross-sectional diameters that lie within the second size distribution; andthe first and second size distributions do not overlap. 35. A method as in claim 29, wherein the the catalyst comprises pores with a pore size in the range from about 5.5 Angstroms to about 6.5 Angstroms. 36. A method as in claim 29, wherein the catalyst comprises pores with a pore size in the range from about 5.9 to about 6.3 angstroms. 37. A method as in claim 29, wherein the catalyst comprises a zeolite catalyst with a biomodal distribution of pore sizes. 38. A method for producing one or more fluid hydrocarbon products from a solid hydrocarbonaceous material comprising: providing the solid hydrocarbonaceous material and one or more catalysts to a fluidized bed reactor, wherein the one or more catalysts comprise silica and alumina in a silica to alumina molar ratio of at least about 30:1, the one or more catalysts comprise pores with a pore size in the range from about 5 to about 100 Angstroms, and the solid hydrocarbonaceous material comprises lignocellulosic biomass;pyrolyzing at least a portion of the hydrocarbonaceous material under reaction conditions sufficient to produce one or more pyrolysis products; andcatalytically reacting at least a portion of the pyrolysis products with the one or more catalysts to produce the one or more fluid hydrocarbon products, wherein the fluid hydrocarbon products comprise olefins and aromatics; andrecovering a product stream comprising the one or more fluid hydrocarbon products from the reactor, wherein the aromatics in the one or more fluid hydrocarbon products comprise benzene, toluene, xylene, naphthalene or a mixture of two or more thereof, an amount of benzene, toluene, xylene, naphthalene or a mixture of two or more thereof in the one or more fluid hydrocarbon products is at least about 10% by weight based on the weight of the hydrocarbonaceous material used in forming the one or more pyrolysis products;wherein a residence time of the solid hydrocarbonaceous material in the reactor is at least about 10 seconds, the residence time being calculated by dividing the volume of the reactor with the volumetric flow rate of hydrocarbonaceous material and the one or more fluid hydrocarbon products exiting the reactor. 39. A method as in claim 38, further comprising separating the one or more fluid hydrocarbon products from the catalyst by passing the catalyst and the one or more fluid hydrocarbon products through a solids separator at a solids separator residence time of at least about 1 second and at a solids separator temperature of greater than about 500° C. 40. A method as in claim 38, wherein the one or more catalysts comprise a silica to alumina molar ratio of from about 30:1 to about 200:1. 41. A method as in claim 38, wherein the one or more catalysts comprise a silica to alumina ratio of from about 30:1 to about 150:1. 42. A method as in claim 38, wherein the one or more catalysts further comprise a metal or an oxide of said metal, wherein the metal comprises nickel, platinum, vanadium, palladium, manganese, cobalt, zinc, copper and/or gallium. 43. A method as in claim 38, wherein the one or more catalysts comprise pores having a pore size between about 5.9 and about 6.3 Angstroms. 44. A method as in claim 38, wherein the one or more catalysts comprise pores having a pore size between about 5.5 and about 6.5 Angstroms. 45. A method as in claim 38, wherein the one or more catalysts have a biomodal distribution of pore sizes. 46. A method as in claim 38, wherein: the one or more catalysts comprise a plurality of pores;at least about 95% of the pores of the one or more catalysts have smallest cross-sectional diameters that lie within a first size distribution or a second size distribution;at least about 5% of the pores of the one or more catalysts have smallest cross-sectional diameters that lie within the first size distribution;at least about 5% of the pores of the one or more catalysts have smallest cross-sectional diameters that lie within the second size distribution; andthe first and second size distributions do not overlap. 47. A method as in claim 38, wherein: the one or more catalysts comprise a plurality of pores;at least about 95% of the pores of the one or more catalysts have smallest cross-sectional diameters that lie within a first distribution and a second distribution, wherein the first distribution is between about 5.9 Angstroms and about 6.3 Angstroms and the second distribution is different from and does not overlap with the first distribution;at least about 5% of the pores of the one or more catalysts have smallest cross-sectional diameters between about 5.9 Angstroms and about 6.3 Angstroms; andat least about 5% of the pores of the one or more catalysts have smallest cross-sectional diameters that lie within the second distribution. 48. A method as in claim 38, wherein: the one or more catalysts comprise a plurality of pores; at least about 95% of the pores of the one or more catalysts have smallest cross-sectional diameters between about 5.9 Angstroms and about 6.3 Angstroms or between about 7 Angstroms and about 100 Angstroms;at least about 5% of the pores of the one or more catalysts have smallest cross-sectional diameters between about 5.9 Angstroms and about 6.3 Angstroms; andat least about 5% of the pores of the one or more zeolite catalysts have smallest cross-sectional diameters between about 7 Angstroms and about 2-90100 Angstroms. 49. A method as in claim 38, wherein the one or more catalysts have one or more metals incorporated therein. 50. The method of claim 38 wherein the silica to alumina molar ratio is at least about 50:1. 51. The method of claim 38 wherein the silica to alumina molar ratio is at least about 150:1. 52. The method of claim 38 wherein the silica to alumina molar ratio is in the range from about 30:1 to about 200:1. 53. The method of claim 38 wherein the silica to alumina molar ratio is in the range from about 50:1 to about 160:1. 54. A method for producing one or more fluid hydrocarbon products from a solid hydrocarbonaceous material comprising: providing the solid hydrocarbonaceous material to a fluidized bed reactor and contacting the solid hydrocarbonaceous material with a zeolite catalyst comprising gallium, wherein the zeolite catalyst comprises pores with a pore size in the range from about 5 to about 100 Angstroms, the zeolite catalyst comprises Si, Al and Ga, a ratio of moles of Si to the sum of moles of Ga and Al in the catalyst is at least about 15:1, and the solid hydrocarbonaceous material comprises lignocellulosic biomass;pyrolyzing at least a portion of the solid hydrocarbonaceous material in the reactor under reaction conditions sufficient to produce one or more pyrolysis products;catalytically reacting in the reactor at least a portion of the one or more pyrolysis products with the zeolite catalyst to produce the one or more fluid hydrocarbon products, wherein the one or more fluid hydrocarbon products comprise one or more aromatic compounds, the aromatic compounds in the one or more fluid hydrocarbon products comprise benzene, toluene, xylene, naphthalene or a mixture of two or more thereof, an amount of benzene, toluene, xylene, naphthalene or a mixture of two or more thereof in the one or more fluid hydrocarbon products is at least about 10% by weight based on the weight of the hydrocarbonaceous material used in forming the one or more pyrolysis products; andrecovering a product stream comprising the one or more fluid hydrocarbon products from the reactor;wherein a residence time of the solid hydrocarbonaceous material in the reactor is at least about 10 seconds, the residence time being calculated by dividing the volume of the reactor with the volumetric flow rate of hydrocarbonaceous material and the one or more fluid hydrocarbon products exiting the reactor. 55. A method for producing one or more fluid hydrocarbon products from a solid hydrocarbonaceous material comprising: providing a solid hydrocarbonaceous material to a fluidized bed reactor and contacting the solid hydrocarbonaceous material with a catalyst comprising a galloaluminosilicate Mordenite Framework Inverted zeolite, wherein the catalyst comprises pores with a pore size in the range from about 5 to about 100 Angstroms and the solid hydrocarbonaceous material comprises lignocellulosic biomass;pyrolyzing at least a portion of the hydrocarbonaceous material in the reactor under reaction conditions sufficient to produce one or more pyrolysis products;catalytically reacting in the reactor at least a portion of the pyrolysis products with the catalyst to produce the one or more fluid hydrocarbon products, wherein the one or more fluid hydrocarbon products comprise one or more aromatic compounds, the one or more aromatic compounds comprise benzene, toluene, xylene, naphthalene or a mixture of two or more thereof, an amount of benzene, toluene, xylene, naphthalene or a mixture of two or more thereof in the one or more fluid hydrocarbon products is at least about 10% by weight based on the weight of the hydrocarbonaceous material used in forming the one or more pyrolysis products; andrecovering a product stream comprising the one or more fluid hydrocarbon products from the reactor;wherein a residence time of the solid hydrocarbonaceous material in the fluidized bed reactor is at least about 10 seconds, the residence time being calculated by dividing the volume of the reactor with the volumetric flow rate of hydrocarbonaceous material and the one or more fluid hydrocarbon products exiting the reactor. 56. A method as in claim 55, wherein the galloaluminosilicate Mordenite Framework Inverted zeolite is in the hydrogen form. 57. A method as in claim 55, wherein a ratio of moles of Si in the galloaluminosilicate zeolite catalyst to the sum of the moles of Ga and Al in the galloaluminosilicate zeolite catalyst is at least about 20:1. 58. A method as in claim 55, wherein a ratio of moles of Si in the galloaluminosilicate zeolite catalyst to the moles of Al in the galloaluminosilicate zeolite catalyst is at least about 10:1. 59. A method as in claim 55, wherein: the catalyst comprises a plurality of catalyst particles, andat least about 50% of the sum of the total volume of catalyst is occupied by particles having maximum cross-sectional dimensions of less than about 1 micron. 60. A method as in claim 55, wherein the one or more fluid hydrocarbon products contain more aromatic compounds than olefinic compounds. 61. A method as in claim 55, wherein the solid hydrocarbonaceous material comprises sugar cane bagasse, glucose, wood, corn stover, or a combination of two or more thereof. 62. A method as in claim 55, wherein the temperature in the reactor is between about 500° C. and about 1000° C. 63. A method as in claim 55, wherein the temperature in the reactor is at least about 700° C. 64. A method as in claim 55, wherein the fluid hydrocarbon product comprises an amount of aromatic compounds that is at least about 15 wt %. 65. A method as in claim 55, wherein the reactor has a volume of at least about 1 liter. 66. A method as in claim 55, wherein the catalyst comprises pores having a pore size from about 5.5 Angstroms to about 6.5 Angstroms. 67. A method as in claim 55, wherein the catalyst comprises pores having a pore size between about 5.9 and about 6.3 Angstroms. 68. A method as in claim 55, wherein the catalyst has a bimodal distribution of pore sizes. 69. A method as in claim 55, wherein: the catalyst comprises a plurality of pores;at least about 95% of the pores of the one or more catalysts have smallest cross-sectional diameters that lie within a first size distribution or a second size distribution;at least about 5% of the pores of the one or more catalysts have smallest cross-sectional diameters that lie within the first size distribution;at least about 5% of the pores of the one or more catalysts have smallest cross-sectional diameters that lie within the second size distribution; andthe first and second size distributions do not overlap. 70. A method for producing one or more fluid hydrocarbon products from a solid hydrocarbonaceous material comprising: providing a solid hydrocarbonaceous material to a fluidized bed reactor and contacting a catalyst, wherein the catalyst comprises silica and alumina in a silica to alumina molar ratio of at least about 30:1, the catalyst comprises pores with a pore size in the range from about 5 to about 100 Angstroms, and the solid hydrocarbonaceous material comprises lignocellulosic biomass;pyrolyzing within the reactor at least a portion of the solid hydrocarbonaceous material under reaction conditions sufficient to produce one or more pyrolysis products;catalytically reacting in the reactor at least a portion of the one or more pyrolysis products using the catalyst under reaction conditions sufficient to produce the one or more fluid hydrocarbon products, wherein the one or more fluid hydrocarbon products comprise an amount of aromatic compounds that is at least 35 wt % of the total amount of the hydrocarbonaceous material used in forming the one or more pyrolysis products and which is calculated as the weight of the aromatic compounds present in the one or more fluid hydrocarbon products divided by the weight of the hydrocarbonaceous material used in forming the one or more pyrolysis products, and the aromatic compounds comprise benzene, toluene, xylene, naphthalene or a mixture of two or more thereof; andrecovering a product stream comprising the one or more fluid hydrocarbon products from the reactor;wherein a residence time of the solid hydrocarbonaceous material in the fluidized bed reactor is at least about 10 seconds, the residence time being calculated by dividing the volume of the reactor with the volumetric flow rate of hydrocarbonaceous material and the one or more fluid hydrocarbon products exiting the reactor. 71. A method as in claim 70, wherein the catalyst comprises a silica to alumina molar ratio of about 30:1 to about 200:1. 72. A method as in claim 70, wherein the catalyst comprises a galloaluminosilicate Mordenite Framework Inverted zeolite. 73. A method for producing one or more fluid hydrocarbon products from a solid hydrocarbonaceous material comprising: feeding a solid hydrocarbonaceous material to a fluidized bed reactor and contacting a catalyst with the solid hydrocarbonaceous material in the reactor, wherein the catalyst comprises porous particles and said particles have a pore size of less than about 100 Angstroms;flowing a fluidization fluid into the reactor;pyrolyzing within the reactor at least a portion of the solid hydrocarbonaceous material to produce one or more pyrolysis products;reacting within the reactor in the presence of the catalyst at least a portion of the one or more pyrolysis products to produce the one or more fluid hydrocarbon products, wherein the one or more fluid hydrocarbon products comprise olefins and aromatics;separating at least a portion of the olefins from the one or more fluid hydrocarbon products to produce a recycle stream comprising the separated olefins and a product stream comprising a remainder of the one or more fluid hydrocarbon products;recovering said product stream; andrecycling at least a portion of the recycle stream to the reactor to increase the amount of aromatic compounds in the one or more fluid hydrocarbon products, wherein the aromatics in the one or more fluid hydrocarbon products comprise benzene, toluene, xylene, naphthalene or a mixture of two or more thereof, an amount of benzene, toluene, xylene, naphthalene or a mixture of two or more thereof in the one or more fluid hydrocarbon products is at least about 10% by weight based on the weight of the hydrocarbonaceous material used in forming the one or more pyrolysis products;wherein a residence time of the fluidization fluid in the reactor is at least about 10 seconds, the residence time being calculated by dividing the volume of the reactor with the volumetric flow rate of the fluidization fluid.