Systems and processes for catalytic pyrolysis of biomass and hydrocarbonaceous materials for production of aromatics with optional olefin recycle, and catalysts having selected particle size for catalytic pyrolysis
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C10G-001/00
C10G-003/00
C10B-049/22
C10B-053/02
C10B-057/06
C10G-001/10
C10G-011/18
C10G-001/02
C07C-045/49
C10G-045/32
C10G-050/00
B01J-029/40
B01J-029/44
B01J-029/46
B01J-029/48
B01J-029/87
출원번호
US-0868423
(2015-09-29)
등록번호
US-9453166
(2016-09-27)
발명자
/ 주소
Huber, George H.
Gaffney, Anne Mae
Jae, Jungho
Cheng, Yu-Ting
출원인 / 주소
University of Massachusetts
대리인 / 주소
Renner, Otto, Boisselle & Sklar, LLP
인용정보
피인용 횟수 :
0인용 특허 :
20
초록▼
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.
대표청구항▼
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 comprises olefins and aromatics, the catalyst comprises pores having a pore size of up to 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;recycling 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, the 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 solid hydrocarbonaceous material fed to the reactor; andseparating 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. 2. A method as in claim 1 wherein a residence time of the catalyst in the solids separator is at least about 1 second. 3. A method as in claim 1 wherein a temperature in the solids separator is at least about 500° C. 4. A method as in claim 1 wherein a temperature within the reactor is between about 500° C. and about 1000° C. 5. A method as in claim 1, wherein the catalyst comprises a zeolite catalyst. 6. A method as in claim 1, wherein the catalyst comprises ZSM-5. 7. A method as in claim 1, wherein the catalyst comprises silica and alumina with a silica to alumina molar ratio of from about 30:1 to about 150:1. 8. A method as in claim 1 wherein the catalyst comprises a metal and/or an oxide of the metal, wherein the metal comprises nickel, platinum, vanadium, palladium, manganese, cobalt, zinc, copper, gallium, or a mixture of two or more thereof. 9. A method as in claim 1 wherein the catalyst comprises a plurality of catalyst particles, at least about 50% of the sum of the total volume of catalyst being occupied by particles having maximum cross-sectional dimensions of less than about 1 micron. 10. A method as in claim 1 wherein the pore size of the catalyst is between about 5 and about 100 Angstroms. 11. A method as in claim 1, wherein the catalyst comprises pores with a bimodal distribution of pore sizes. 12. A method as in claim 1, wherein: the catalyst comprises a plurality of pores;at least about 95% of the pores of the catalyst have cross-sectional diameters that lie within a first size distribution or a second size distribution;at least about 5% of the pores of the catalyst have cross-sectional diameters that lie within the first size distribution;at least about 5% of the pores of the catalyst have cross-sectional diameters that lie within the second size distribution; andthe first and second size distributions do not overlap. 13. A method as in claim 1, wherein: the catalyst comprises a plurality of pores;at least about 95% of the pores of the catalyst have 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 catalyst have cross-sectional diameters between about 5.9 Angstroms and about 6.3 Angstroms; andat least about 5% of the pores of the catalyst have cross-sectional diameters that lie within the second distribution. 14. A method as in claim 1, wherein: the catalyst comprises a plurality of pores;at least about 95% of the pores of the catalyst have 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 catalyst have cross-sectional diameters between about 5.9 Angstroms and about 6.3 Angstroms; andat least about 5% of the pores of the catalyst have cross-sectional diameters between about 7 Angstroms and about 100 Angstroms. 15. A method as in claim 1, 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. 16. A method as in claim 1 wherein the catalyst comprises one or more agglomerates comprising a plurality of catalyst particles, wherein the catalyst particles having an average cross-sectional dimension of less than about 5 microns. 17. A method as in claim 1 wherein the catalyst comprises a plurality of solid catalytic particles, wherein the plurality of solid catalytic particles having a particle size distribution with a standard deviation of the maximum cross-sectional dimensions of the particles of less than about 50%. 18. A method as in claim 1, wherein the solid hydrocarbonaceous material further comprises plastic waste, recycled plastics, agricultural solid waste, municipal solid waste, food waste, animal waste, carbohydrates, or a mixture of two or more thereof. 19. A method as in claim 1, wherein the solid hydrocarbonaceous material further comprises xylitol, glucose, cellobiose, hemi-cellulose, lignin, or a mixture of two or more thereof. 20. A method as in claim 1, wherein the solid hydrocarbonaceous material comprises sugar cane bagasse, glucose, wood, corn stover, or a mixture of two or more thereof. 21. A method as in claim 1 wherein a pressure in the reactor is between about 1 and about 4 atmospheres. 22. A method as in claim 1 wherein a pressure in the reactor is at least about 4 atmospheres. 23. A method as in claim 1 wherein the one or more fluid hydrocarbon products comprise one or more aromatic compounds, wherein the one or more aromatic compounds comprising benzene, toluene, xylene, naphthalene or a mixture of two or more thereof, the 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. 24. A method as in claim 1 comprising feeding a reactant mixture comprising the solid hydrocarbonaceous material and the catalyst to the reactor. 25. A method as in claim 1 comprising feeding the solid hydrocarbonaceous material to the reactor, and separately feeding the catalyst to the reactor. 26. A method as in claim 1 comprising feeding a mixture comprising the solid hydrocarbonaceous material and one or more olefins to the reactor. 27. A method as in claim 1 comprising feeding a mixture comprising the solid hydrocarbonaceous material, the catalyst and one or more olefins to the reactor. 28. A method as in claim 1 wherein the solid hydrocarbonaceous material contains moisture, the method further comprising removing moisture from the solid hydrocarbonaceous material prior to feeding the solid hydrocarbonaceous material to the reactor. 29. A method as in claim 1 wherein the solid hydrocarbonaceous material is ground to produce solid hydrocarbonaceous particles, the solid hydrocarbonaceous particles being fed to the reactor. 30. A method as in claim 1 wherein a temperature of the solid hydrocarbonaceous material being fed to the reactor is below about 300° C. 31. A method as in claim 1 wherein the solid hydrocarbonaceous material and a fluidization fluid are fed to the reactor, wherein the fluidization fluid comprising carbon monoxide and/or carbon dioxide. 32. A method as in claim 1 wherein the one or more pyrolysis products comprises one or more unsaturated pyrolysis products, the method further comprising hydrogenating at least a portion of the one or more unsaturated pyrolysis products to form one or more hydrogenated pyrolysis products. 33. A method as in claim 1 wherein the one or more fluid hydrocarbon products comprises one or more olefins, the method further comprising oligomerizing at least a portion of the one or more olefins to form one or more aromatic compounds. 34. A method as in claim 1 wherein the one or more fluid hydrocarbon products comprises one or more olefins, the method further comprising carbonylating at least a portion of the one or more olefins to form one or more carbonyl compounds. 35. A method as in claim 1 wherein the one or more fluid hydrocarbon products comprises one or more vapors, the method further comprising condensing at least a portion of the one or more vapors in a condenser.
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이 특허에 인용된 특허 (20)
Haag Werner O. (Lawrenceville NJ) Rodewald Paul G. (Rocky Hill NJ) Weisz Paul B. (Yardley PA), Conversion of biological material to liquid fuels.
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