Catalytic pyrolysis of solid biomass and related biofuels, aromatic, and olefin compounds

A method for producing one or more fluid hydrocarbon products from a solid hydrocarbonaceous material comprising:

• providing a solid catalyst in a reactor;
• providing a solid hydrocarbonaceous material in the reactor;
• pyrolyzing within the reactor at least a portion of the hydrocarbonaceous material under reaction conditions sufficient to produce one or more pyrolysis products;
• catalytically reacting at least a portion of the one or more pyrolysis products using the solid catalyst under reaction conditions sufficient to produce the one or more fluid hydrocarbon products;
• and
• feeding the one or more hydrocarbon products and the catalyst to a separator, further reacting the hydrocarbon products in the separator, and separating the one or more hydrocarbon products from the catalyst at a separator residence time of at least about 10 seconds and at a separator temperature of greater than about 500° C., the separator residence time being calculated by dividing the volume of the separator with the volumetric flow rate of the catalyst through the separator.

A method for producing one or more fluid hydrocarbon products from a hydrocarbonaceous material comprising:

• providing a hydrocarbonaceous material in a first reactor comprising a circulating fluidized bed reactor or a turbulent fluidized bed reactor;
• pyrolyzing within the first reactor at least a portion of the hydrocarbonaceous material under reaction conditions sufficient to produce one or more pyrolysis products;
• and
• catalytically reacting at least a portion of the one or more pyrolysis products in a second reactor using a catalyst under reaction conditions sufficient to produce one or more fluid hydrocarbon products;
• wherein the residence time of the hydrocarbon material in the second reactor is at least about 10 seconds, the residence time in the second reactor being calculated by dividing the volume of the second reactor with the volumetric flow rate of the hydrocarbonaceous material and fluid hydrocarbon product exiting the second reactor.

A method for producing one or more fluid hydrocarbon products from a solid hydrocarbonaceous material comprising:

• providing a solid hydrocarbonaceous material in a first reactor comprising a fluidized bed reactor;
• pyrolyzing within the first reactor at least a portion of the hydrocarbonaceous material under reaction conditions sufficient to produce one or more pyrolysis products;
• and
• catalytically reacting at least a portion of the one or more pyrolysis products in a second reactor using a catalyst under reaction conditions sufficient to produce the one or more fluid hydrocarbon products;
• wherein the residence time of the pyrolysis products in the second reactor is at least about 60 seconds, the residence time in the second reactor being calculated by dividing the volume of the second reactor with the volumetric flow rate of the pyrolysis products and fluid hydrocarbon product exiting the second reactor.

A method for producing one or more fluid hydrocarbon products from a solid hydrocarbonaceous material comprising:

• introducing a fluidization fluid into a fluidized bed reactor, the fluidization fluid having an average fluidization fluid residence time of at least about 4-10 seconds in the reactor;
• providing a solid catalyst in the fluidized bed reactor;
• feeding a solid hydrocarbonaceous material to the fluidized bed reactor;
• pyrolyzing within the fluidized bed reactor at least a portion of the hydrocarbonaceous material under reaction conditions sufficient to produce one or more pyrolysis products, wherein the fluidized bed reactor has a temperature of about 500° C. to about 1000° C.;
• and
• catalytically reacting at least a portion of the one or more pyrolysis products using the solid catalyst under reaction conditions sufficient to produce the one or more fluid hydrocarbon products;
• wherein the residence time of the 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 the hydrocarbonaceous material and fluid hydrocarbon product exiting the reactor.

A method for producing a fluid hydrocarbon product from a solid hydrocarbonaceous material comprising:

• providing a solid hydrocarbonaceous material and a catalyst in a reactor;
• pyrolyzing within the reactor at least a portion of the hydrocarbonaceous material under reaction conditions sufficient to produce one or more pyrolysis products;
• and
• catalytically reacting at least a portion of the one or more pyrolysis products using the catalyst under reaction conditions sufficient to produce the fluid hydrocarbon product, wherein the fluid hydrocarbon product comprises an amount of aromatic compounds that is at least 15 wt % of the total amount of the solid hydrocarbonaceous material used in forming the pyrolysis products and which is calculated as the weight of the aromatic compounds present in the fluid hydrocarbon product divided by the weight of the hydrocarbonaceous material used in forming the pyrolysis products;
• wherein the residence time of the 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 the hydrocarbonaceous material and fluid hydrocarbon product exiting the reactor.

A method for producing a fluid hydrocarbon product from a solid hydrocarbonaceous material comprising:

• providing a solid hydrocarbonaceous material and a catalyst in a reactor;
• pyrolyzing within the reactor at least a portion of the hydrocarbonaceous material under reaction conditions sufficient to produce one or more pyrolysis products;
• and
• catalytically reacting at least a portion of the one or more pyrolysis products using the catalyst under reaction conditions sufficient to produce the fluid hydrocarbon product, wherein the fluid hydrocarbon product comprises an amount of olefin compounds that is at least about 7 wt % of the total amount of the hydrocarbonaceous material used in forming the pyrolysis products and which is calculated as the weight of the olefin compounds present in the fluid hydrocarbon product divided by the weight of the hydrocarbonaceous material used in forming the pyrolysis products;
• wherein the residence time of the 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 the hydrocarbonaceous material and fluid hydrocarbon product exiting the reactor.

A method for selectively producing one or more fluid hydrocarbon products from a hydrocarbonaceous material comprising:

• providing a solid hydrocarbonaceous material and a zeolite catalyst comprising a silica to alumina molar ratio of from about 30:1 to about 150:1 within a reactor;
• pyrolyzing within the reactor at least a portion of the hydrocarbonaceous material under reaction conditions sufficient to produce one or more pyrolysis products, wherein the hydrocarbonaceous material and catalyst are heated at a heating rate of greater than about 50° C./s, and wherein the reactor has a volume of at least about 1 liter;
• and
• catalytically reacting at least a portion of the one or more pyrolysis products using the catalyst under reaction conditions sufficient to selectively produce said one or more fluid hydrocarbon products and to minimize coke production;
• wherein the residence time of the 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 the hydrocarbonaceous material and fluid hydrocarbon product exiting the reactor.

A method for producing one or more fluid hydrocarbon products from a solid hydrocarbonaceous material comprising:

• providing a solid catalyst in a circulating fluidized bed reactor;
• feeding a solid hydrocarbonaceous material to the circulating fluidized bed reactor, such that the mass ratio of the catalyst to the hydrocarbonaceous material in the feed is from about 0.5:1 to about 20:1;
• pyrolyzing within the circulating fluidized bed reactor at least a portion of the hydrocarbonaceous material under reaction conditions sufficient to produce one or more pyrolysis products, wherein the reaction takes place at a temperature of about 500° C. to about 1000° C.;
• and
• catalytically reacting at least a portion of the one or more pyrolysis products using the solid catalyst under reaction conditions sufficient to produce the one or more fluid hydrocarbon products;
• wherein the residence time of the 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 the hydrocarbonaceous material and fluid hydrocarbon product exiting the reactor.

A method for producing one or more fluid hydrocarbon products from a solid hydrocarbonaceous material comprising:

• providing a solid catalyst in a circulating fluidized bed reactor;
• feeding a solid hydrocarbonaceous material to the circulating fluidized bed reactor, wherein the mass ratio of the catalyst to the hydrocarbonaceous material in the feed is from about 0.5:1 to about 20:1;
• pyrolyzing within the circulating fluidized bed reactor at least a portion of the hydrocarbonaceous material under reaction conditions sufficient to produce one or more pyrolysis products, wherein the mass-normalized space velocity of the hydrocarbonaceous material is between about 0.01 hour−1 and about 10 hours−1;
• and
• catalytically reacting at least a portion of the one or more pyrolysis products using the solid catalyst under reaction conditions sufficient to produce the one or more fluid hydrocarbon products;
• wherein the residence time of the 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 the hydrocarbonaceous material and fluid hydrocarbon product exiting the reactor.

A method for producing one or more fluid hydrocarbon products from a solid hydrocarbonaceous material comprising:

• providing a solid hydrocarbonaceous material and one or more catalysts in a reactor, wherein
• 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;
• and
• the first and second size distributions do not overlap;
• and
• pyrolyzing within the reactor at least a portion of the hydrocarbonaceous material under reaction conditions sufficient to produce one or more pyrolysis products and catalytically reacting at least a portion of the pyrolysis products with the catalysts to produce the one or more hydrocarbon products and at least partially deactivated catalyst;
• wherein the residence time of the 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 the hydrocarbonaceous material and fluid hydrocarbon product exiting the reactor.

A method for producing one or more fluid hydrocarbon products from a solid hydrocarbonaceous material comprising:

• providing a solid hydrocarbonaceous material and one or more catalysts in a reactor, wherein
• 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;
• and
• at least about 5% of the pores of the one or more catalysts have smallest cross-sectional diameters that lie within the second distribution;
• and
• pyrolyzing within the reactor at least a portion of the solid hydrocarbonaceous material under reaction conditions sufficient to produce one or more pyrolysis products and catalytically reacting at least a portion of the pyrolysis products with the one or more catalysts to produce the one or more fluid hydrocarbon products and at least partially deactivated catalyst
• wherein the residence time of the 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 the hydrocarbonaceous material and fluid hydrocarbon product exiting the reactor.

A method for producing a fluid hydrocarbon product from a solid hydrocarbonaceous material comprising:

• providing a composition comprising a solid catalyst and a solid hydrocarbonaceous material to a reactor, wherein the mass ratio of the catalyst to the hydrocarbonaceous material in the composition is between about 0.5:1 and about 20:1;
• heating the composition provided within the reactor, wherein the residence time of the hydrocarbonaceous material in the reactor is between about 1 minute and about 4 minutes;
• pyrolyzing within the reactor at least a portion of the hydrocarbonaceous material to produce pyrolysis products;
• and
• catalytically reacting at least a portion of the pyrolysis products with the solid catalyst to produce the fluid hydrocarbon product.

A method for selectively producing one or more fluid hydrocarbon products from a solid hydrocarbonaceous material comprising:

• providing a solid hydrocarbonaceous material comprising a first component and a second component in a reactor, wherein the first and second components are different;
• providing first and second catalysts in 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;
• and
• pyrolyzing within the reactor at least a portion of the hydrocarbonaceous material under reaction conditions sufficient to produce one or more pyrolysis products and catalytically reacting at least a portion of the pyrolysis products with the first and second catalysts to produce the one or more hydrocarbon products and at least partially deactivated catalyst.