Process for producing renewable biofuel from a pyrolyzed biomass containing bio-oil stream
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C10L-001/02
C10G-001/06
C10G-003/00
C10G-031/09
C10L-001/06
출원번호
US-0553742
(2012-07-19)
등록번호
US-9303213
(2016-04-05)
발명자
/ 주소
Lin, Ronny W.
Bauer, Lorenz J.
출원인 / 주소
KiOR, LLC
대리인 / 주소
Jones, John Wilson
인용정보
피인용 횟수 :
1인용 특허 :
13
초록▼
A process for preparing a renewable biofuel consists of subjecting a bio-oil mixture to deoxygenation in a hydrotreater and then separating hydrocarbon fractions from the deoxygenated product to form the biofuel. The bio-oil mixture contains a bio-oil feedstream and a treated bio-oil feed. The treat
A process for preparing a renewable biofuel consists of subjecting a bio-oil mixture to deoxygenation in a hydrotreater and then separating hydrocarbon fractions from the deoxygenated product to form the biofuel. The bio-oil mixture contains a bio-oil feedstream and a treated bio-oil feed. The treated bio-oil feed is a stream from which undesirable heavy materials and solid materials have been removed.
대표청구항▼
1. A process for producing a renewable biofuel from a pyrolyzed biomass containing bio-oil stream and a treated bio-oil feed, the process comprising: (a) mixing in a mixing zone at least a portion of the treated bio-oil feed with the pyrolyzed biomass containing bio-oil stream to form a bio-oil mixt
1. A process for producing a renewable biofuel from a pyrolyzed biomass containing bio-oil stream and a treated bio-oil feed, the process comprising: (a) mixing in a mixing zone at least a portion of the treated bio-oil feed with the pyrolyzed biomass containing bio-oil stream to form a bio-oil mixture;(b) separating water and at least a portion of the heavy fraction from the bio-oil mixture produced in the mixing zone to render a non-heavy fraction of the bio-oil mixture;(c) subjecting the non-heavy fraction of the bio-oil mixture produced in the mixing zone to deoxygenation in a hydrotreater to form a separated hydrotreated product and, optionally, a partial deoxygenated intermediate and removing the separated hydrotreated product and the optional partial deoxygenated intermediate from the hydrotreater;(d) removing produced water from the separated hydrotreated product;(e) subjecting the separated hydrotreated product of step (c) to fractionation to render oil having a boiling point in excess of 650° F. and at least one hydrocarbon fraction having a boiling point less than 650° F. and;(f) generating renewable biofuel from the separated fractionswherein the treated bio-oil feed is at least one of the following: (i) at least a portion of the separated hydrotreated product; or(ii) at least a portion of the at least one hydrocarbon fraction having a boiling point less than 650° F.; or(iii) a partial deoxygenated intermediate. 2. The process of claim 1, wherein the at least one hydrocarbon fraction having a boiling point less than 650° F. comprises (i) naphtha having a boiling point between from 150° F. to 350° F. and (ii) a hydrotreated distillate having a boiling point between from 320° F. to less than 650° F. 3. The process of claim 2, wherein the treated bio-oil feed is at least a portion of the naphtha. 4. The process of claim 2, wherein the treated bio-oil feed is at least a portion of the hydrotreated distillate. 5. The process of claim 1, wherein the treated bio-oil feed is at least a portion of the separated hydrotreated product. 6. The process of claim 1, further comprising mixing the pyrolyzed biomass containing bio-oil stream with a hydrotreated bio-oil feed comprising at least one member selected from the group consisting of: (i) at least a portion of the separated hydrotreated product;(ii) at least a portion of the at least one hydrocarbon fraction having a boiling point less than 650° F.; and(iii) a partial deoxygenated intermediate to form a bio-oil mixture and then repeating steps (b), (c), (d) and (e). 7. The process of claim 6, wherein the process is continuous. 8. The process of claim 6, further comprising, prior to repetitive step (c), fractionating the non-heavy fraction of the bio-oil mixture to yield a bio-naphtha stream and then diluting the bio-oil mixture with the bio-naphtha stream. 9. The process of claim 6, wherein the at least one hydrocarbon fraction is a light hydrocarbon distillate having a boiling point between from 320° F. to less than 650° F. 10. The process of claim 6, wherein the at least one hydrocarbon fraction is hydrotreated naphtha having a boiling point between 150° F. and 350° F. 11. The process of claim 1, wherein the pyrolyzed biomass containing bio-oil stream is derived from thermal pyrolysis. 12. The process of claim 1, wherein the bio-oil mixture contains bio-naphtha. 13. The process of claim 1, further comprising, after separating the at least a portion of the heavy fraction from the bio-oil mixture, removing residual solids from the bio-oil mixture. 14. The method of claim 13, wherein the residual solids are removed by polishing filtration. 15. A process for producing a renewable biofuel from a pyrolyzed biomass containing bio-oil stream and a hydrotreated bio-oil feed, the process comprising: (a) mixing in a mixing zone at least a portion of the hydrotreated bio-oil feed with the pyrolyzed biomass containing bio-oil stream to form a bio-oil wherein the pyrolyzed biomass containing bio-oil stream contains coke-forming heavy materials;(b) separating water and the coke-forming heavy materials from the bio-oil mixture produced in the mixing zone to form a separated bio-oil mixture;(c) subjecting the separated bio-oil mixture to deoxygenation in a hydrotreater to render a separated hydrotreated product and, optionally, a partial deoxygenated intermediate;(d) removing the optionally rendered partial deoxygenated intermediate from the hydrotreater;(e) removing produced water from the separated hydrotreated product of step (c) to render a treated separated hydrotreated product;(f) subjecting the treated separated hydrotreated product to fractionation and obtaining hydrocarbon distillate fractions from the treated separated hydrotreated product; and(g) generating renewable biofuel from at least one of the hydrocarbon distillate fractionswherein at least a portion of the hydrotreated bio-oil feed is selected from a member of the group consisting of: (i) the treated separated hydrotreated product;(ii) one or more of the hydrocarbon distillate fractions from the treated separated hydrotreated product; and(iii) the partial deoxygenated intermediate. 16. The process of claim 15, wherein the hydrotreated bio-oil feed comprises the hydrocarbon distillate fraction containing naphtha. 17. The process of claim 15, wherein at least a portion of the hydrotreated bio-oil feed is the treated separated hydrotreated product. 18. The process of claim 15, wherein the pyrolyzed biomass containing bio-oil stream is derived from thermal pyrolysis. 19. The process of claim 15, further comprising, prior to step (c), fractionating the separated bio-oil mixture to obtain a bio-naphtha stream and then diluting the bio-oil mixture with the fractionated bio-naphtha stream. 20. A process for producing a renewable biofuel from a pyrolyzed biomass containing bio-oil stream comprising: (a) mixing the pyrolyzed biomass containing bio-oil stream with a hydrotreated stream to render a bio-oil mixture;(b) deoxygenating the bio-oil mixture in a hydrotreater having a catalytic hydrotreating bed;(c) separating two or more hydrocarbon streams from the deoxygenated stream; and(d) generating the renewable biofuel from at least one of the separated hydrocarbon streams of step (c)wherein, prior to step (b), materials capable of plugging the catalytic hydrotreating bed are removed from the bio-oil mixture wherein said materials comprise inorganic oxides, clays, catalyst fines, salts of phenolic or organic acids, polar nitrogen compounds, char, phenolic oligomers, aldol condensation products, olefin-derived materials or a mixture thereof. 21. The process of claim 20, wherein: (i) at least a portion of one of the separated hydrocarbon streams of step (c) is mixed with a bio-oil stream to form a bio-oil mixture; and(ii) repeating steps (b), (c) and (d)and further wherein, prior to each repetition of step (b), the materials capable of plugging the catalytic hydrotreating bed are removed from the bio-oil mixture. 22. The process of claim 21, wherein the process is a continuous process. 23. The process of claim 20, wherein the pyrolyzed biomass containing bio-oil stream contains bio-naphtha. 24. The process of claim 20, wherein at least one of the separated hydrocarbon streams contains naphtha. 25. The process of claim 20, wherein, prior to step (c), a portion of the deoxygenated mixture is mixed with the pyrolyzed biomass containing bio-oil stream as the hydrotreated product. 26. A process for producing renewable biofuel from bio-oil comprising: (a) subjecting biomass to pyrolysis in a biomass conversion unit to render a pyrolyzed biomass containing bio-oil stream and then mixing at least a partially deoxygenated hydrotreated bio-oil stream with the pyrolyzed biomass containing bio-oil stream in an in-line mixer to form a bio-oil mixture;(b) removing at least a portion of materials having a boiling point in excess of 650° F. from the bio-oil mixture to render a separated bio-oil mixture;(c) at least partially deoxygenating the separated bio-oil mixture of step (b) in a hydrotreater having a catalytic hydrotreating bed;(d) separating the product of step (c) into one or more light hydrocarbon fractions; and(e) generating biofuel from one or more of the one or more light hydrocarbon fractions of step (d). 27. The process of claim 26, wherein the one or more light hydrocarbon fractions of step (d) are mixed with a pyrolyzed biomass bio-oil containing stream to form a bio-oil mixture and further wherein steps (b), (c) and (d) are repeated. 28. The process of claim 27, wherein the process is continuous. 29. A process for producing biofuel from bio-oil comprising: (a) subjecting biomass to pyrolysis in a biomass conversion unit to form a pyrolyzed biomass containing bio-oil stream and then mixing the pyrolyzed biomass containing bio-oil stream with a hydrotreated stream to form a bio-oil mixture, the hydrotreated stream comprising a stream which, prior to being hydrotreated, has been pre-treated to remove materials having a boiling point greater than 650° F.;(b) removing materials having a boiling point greater than 650° F. from the bio-oil mixture to form a separated bio-oil mixture;(c) hydrotreating the separated bio-oil mixture of step (b) to produce a deoxygenated stream;(d) separating from the deoxygenated stream (i) one or more light hydrocarbon streams having a boiling point less than about 650° F.; and (ii) hydrocarbons having a boiling point in excess of about 650° F.; and(e) generating biofuel from at least a portion of the one or more separated light hydrocarbon streams of step (d). 30. The process of claim 29, further comprising mixing at least a portion of the one or more light hydrocarbon streams of step (d) with the pyrolyzed biomass containing bio-oil stream and forming a bio-oil mixture and then repeating steps (b), (c) and (d). 31. The process of claim 30, wherein the process is a continuous process. 32. The process of claim 29, wherein the bio-oil mixture contains bio-naphtha. 33. The process of claim 30, wherein the one or more light hydrocarbon streams comprise (i) naphtha having a boiling between 150° F. and 350° F. and (ii) a hydrocarbon distillate having a boiling point between from 320° F. to less than 650° F. 34. The process of claim 30, wherein the light hydrocarbon stream is naphtha. 35. The process of claim 1, wherein the temperature in the mixing zone is between 86° F. and 302° F. 36. A process for producing a renewable biofuel from a pyrolyzed biomass containing bio-oil stream comprising: (a) mixing the pyrolyzed biomass containing bio-oil stream with a hydrotreated stream to render a bio-oil mixture;(b) removing heavy materials and solids from the bio-oil mixture to render a separated bio-oil, wherein the heavy materials and solids are selected from the group consisting of phenolic oligomers, aldol condensation products, olefins, olefin derivatives, polar nitrogen compounds, char and inorganic solids and mixtures thereof;(c) deoxygenating the separated bio-oil mixture in a hydrotreater having a catalytic hydrotreating bed;(d) separating two or more hydrocarbon streams from the deoxygenated stream; and(e) generating the renewable biofuel from at least one of the separated hydrocarbon streams of step (d). 37. A process for producing a renewable biofuel from bio-oil comprising: (a) pyrolyzing biomass in a biomass conversion unit to render a pyrolyzed biomass stream containing bio-oil and solids;(b) diluting the concentration of solids in the biomass stream by introducing a hydrotreated stream derived from biomass to render a bio-oil mixture;(c) separating the solids from the bio-oil mixture to produce a separated bio-oil containing stream;(d) deoxygenating the separated bio-oil containing stream in a hydrotreater having a catalytic hydrotreating bed;(e) separating two or more hydrocarbon streams from the deoxygenated stream; and(f) generating the renewable biofuel from at least one of the separated hydrocarbon streams of step (d). 38. The process of claim 37, wherein the solids in the pyrolyzed biomass containing bio-oil stream include coke. 39. The process of claim 1, wherein the hydrotreated bio-oil feed is the partial deoxygenated intermediate. 40. The process of claim 1, wherein the pyrolyzed biomass containing bio-oil stream is derived from catalytic thermolysis. 41. The process of claim 15, wherein the pyrolyzed biomass containing bio-oil stream is derived from catalytic thermolysis. 42. The process of claim 33, wherein the pyrolyzed biomass containing bio-oil stream is derived from catalytic thermolysis. 43. The process of claim 1, wherein a partial deoxygenated intermediate is formed in the hydrotreater and further wherein the separated hydrotreated product removed from the hydrotreater contains the partial deoxygenated intermediate.
Gallivan Robert M. (Erie PA) Matschei Peter K. (Plainsboro NJ), Fractionation of oil obtained by pyrolysis of lignocellulosic materials to recover a phenolic fraction for use in making.
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Taylor James L. (Naperville IL) Beaton William I. (Wheaton IL) So Bernard Y. C. (Wheaton IL) Kolstad Jeffrey J. (Wayzata MN), Resid hydrotreating using solvent extraction and deep vacuum reduction.
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