Aldose-ketose transformation for separation and/or chemical conversion of C6 and C5 sugars from biomass materials
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C12P-019/24
B01J-019/00
C07H-001/08
C07H-003/02
C13K-013/00
C12M-001/12
C12M-001/00
출원번호
US-0641849
(2011-04-19)
등록번호
US-9242222
(2016-01-26)
국제출원번호
PCT/US2011/033030
(2011-04-19)
§371/§102 date
20121112
(20121112)
국제공개번호
WO2011/133536
(2011-10-27)
발명자
/ 주소
Varanasi, Sasidhar
Relue, Patricia
Li, Bin
출원인 / 주소
The University of Toledo
대리인 / 주소
MacMillan, Sobanski & Todd, LLC
인용정보
피인용 횟수 :
0인용 특허 :
14
초록
Systems for converting aldose sugars to ketose sugars and separating and/or concentrating these sugars using differences in the sugars' abilities to bind to specific affinity ligands are described.
대표청구항▼
1. A method for converting an aldose in a biomass hydrolysate to its ketose isomer, comprising: adjusting a pH of a saccharified biomass hydrolysate containing one or more aldose sugars to a value between about 7.5 and about 9, to produce a pH-adjusted hydrolysate;contacting the pH-adjusted hydrolys
1. A method for converting an aldose in a biomass hydrolysate to its ketose isomer, comprising: adjusting a pH of a saccharified biomass hydrolysate containing one or more aldose sugars to a value between about 7.5 and about 9, to produce a pH-adjusted hydrolysate;contacting the pH-adjusted hydrolysate with an isomerization catalyst, wherein at least a portion of the aldose sugar in the pH-adjusted hydrolysate is converted to its ketose isomer, to produce an isomerized hydrolysate;contacting the ketose isomer in the isomerized hydrolysate with an aryl boronic acid (ABA) at a pH in the range of from 7.5 to 8.5 to form a complex of ketose-conjugate base form of the ABA; wherein the contacting comprises bringing the isomerized hydrolysate into contact with an immiscible organic phase that dissolves the ABA and a lipophilic salt (QX), and allowing the ketose in the isomerized hydrolysate to be extracted into the immiscible organic phase via ester formation with a conjugate base form of the ABA that is coupled via ion pair formation with Q+, thereby reducing the concentration of ketose in the isomerized hydrolysate and forming a ketose-rich organic phase, in turn shifting the aldose/ketose equilibrium in favor of more ketose formation in the pH-adjusted hydrolysate;preparing a low pH medium having a pH in the range of from about 2 to about 4.5, that contains an acid HX, wherein X is the same anion as X in the lipophilic salt (QX);bringing the low pH medium into contact with the ketose-rich organic phase; wherein, at the low pH, the ketose and hydroxyl ions are released into the low pH medium and the ABA is converted to its non-ionic conjugate acid; and, wherein, at the same time, the Q+ ion that formed the ion pair combines with an X− ion from the low pH medium to reform the lipophilic salt; andrecovering the ketose from the organic phase into the low pH medium as a concentrated ketose-rich solution. 2. The method of claim 1, including controlling the volume of the low pH medium such that the concentration of ketose in the ketose-rich medium is higher than the initial concentration of aldose in the hydrolysate. 3. The method of claim 1, further including reusing the organic phase containing the ABA and the lipophilic salt for a subsequent batch of hydrolysate. 4. The method of claim 1, wherein the steps of contacting the ketose isomer in the isomerized hydrolysate with ABA, and bringing the low pH medium into contact with the ketose-rich organic phase, are carried out using a micro-porous hollow fiber contactor. 5. The method of claim 4, wherein the micro-porous hollow fiber contactor comprises a shell having a first set of porous hollow fibers adapted for carrying the isomerized hydrolysate; and a second set of porous hollow fibers adapted for carrying the low-pH medium; the shell being configured for containing the organic extraction phase in a shell-side space substantially surrounding the first and second sets of fibers. 6. The method of claim 5, wherein the ketose is transported from the hydrolysate to the immiscible organic phase and from the organic phase to the low-pH medium, wherein the transport of the ketose is facilitated by ABA and QX combination dissolved in the immiscible organic phase. 7. The method of claim 5, wherein the first and second sets of micro-porous hollow fibers are commingled within the shell. 8. The method of claim 5, wherein the saccharified biomass hydrolysate contains glucose and xylose, and the method comprises: passing the hydrolysate through a packed bed reactor containing immobilized xylose isomerase (XI) or solid acid/base catalyst;allowing the isomerized hydrolysate to flow through the first set of fibers within the micro-porous hollow fiber contactor, the isomerized hydrolysate coming into contact with the immiscible organic phase containing lipophilic ABA and a lipophilic salt (QX) that fills the shell;extracting the xylulose in the isomerized hydrolysate, wherein the pH of the isomerized hydrolysate is in the range of from 7.5 to 8.5, into the organic phase via ester formation with a conjugate base form of the ABA coupled by ion pair formation with Q+, thereby reducing concentration of xylulose in the hydrolysate, and shifting the xylose/xylulose equilibrium in favor of more xylulose formation;concurrently with the extracting, allowing the low pH medium to flow through the second set of fibers and contact the organic phase contained on the shell side; whereby: the xylulose and hydroxyl ions attached to the ABA are released into the low pH medium, the ABA is re-converted to its non-ionic conjugate acid, andthe Q+ ion, which formed the ion pair with ABA, combines with an X− ion from the low pH medium to re-form the lipophilic salt. 9. The method of claim 1, including selecting an ABA having a property to enhance selectivity for a specific sugar. 10. The method of claim 1, further including controlling the volume of the low pH medium such that the ketose concentration in the recovered solution is higher than the aldose concentration in the saccharified biomass hydrolysate. 11. The method of claim 1, wherein both glucose and xylose from the hydrolysate are simultaneously isomerized by the isomerization catalyst into ketoses, the ketoses are extracted into the organic phase via binding to the ABA and QX, and the ketoses are recovered from the organic phase via back-extraction into the low pH medium while leaving behind other inhibitory compounds in the biomass hydrolysate. 12. The method of claim 1, wherein a micro-porous hollow fiber contactor physically separates the ketose-rich organic phase from the low pH medium during the ketose recovery. 13. The method of claim 1, wherein the step of contacting the pH-adjusted hydrolysate with an isomerization catalyst comprises passing the pH-adjusted hydrolysate through a packed bed reactor containing the isomerization catalyst, wherein the isomerization catalyst facilitates conversion of glucose to fructose. 14. The method of claim 1, wherein the pH of the recovered ketose is adjusted slightly to a pH suitable for converting the ketose to lactic acid, succinic acid, or fumaric acid by native microorganisms. 15. The method of claim 1, wherein the isomerization catalyst preferentially isomerizes xylose into xylulose compared to glucose into fructose, the ABA preferentially binds to ketoses compared to aldoses, and the system is used to separate C5 sugars from C6 sugars. 16. The method of claim 1, wherein the pH of the recovered ketose corresponds to a pH suitable for dehydration of the ketose to furans via an acid-catalyzed chemical reaction. 17. The method of claim 1, wherein the isomerization catalyst comprises xylose isomerase (XI) particles that facilitate the isomerization of both glucose and xylose. 18. The method of claim 1, comprising: a first micro-porous hollow fiber contactor having a lumen side and a shell side, wherein the hydrolyzate flows through the lumen-side in the first micro-porous hollow fiber contactor and the immiscible organic phase flows through the shell-side; anda second micro-porous hollow fiber contactor that physically separates the ketose-rich organic phase from the low pH medium during ketose recovery. 19. The method of claim 1, wherein the saccharified biomass hydrolysate is a lignocellulosic biomass hydrolysate. 20. The method of claim 19, wherein one or more of the ABA, the pH, and temperature of the hydrolysate, are altered to selectively isomerize and extract one or more specific sugars. 21. The method of claim 1, wherein the ABA is present in an immiscible organic phase that is physically separated by a permeable device from the isomerized hydrolysate, the permeable device allowing transport of the sugar from the isomerized hydrolysate into the immiscible organic phase, while substantially preventing dispersion of the immiscible organic phase in the isomerized hydrolysate. 22. The method of claim 7, wherein the immiscible organic phase comprises one or more of octanol, ethyl acetate, dichloromethane, o-nitrophenyl octyl ether (NPOE), or diethyl ether. 23. The method of claim 21, wherein the permeable device is a micro-porous hollow fiber contactor. 24. The method of claim 1, wherein the step of contacting the pH-adjusted-hydrolysate with an isomerization catalyst comprises passing the pH-adjusted hydrolysate through a packed bed reactor containing the isomerization catalyst, wherein the isomerization catalyst facilitates conversion of xylose into xylulose. 25. The method of claim 24, wherein the packed bed reactor is connected in a loop to a micro-porous hollow fiber contactor having a shell side and a fiber side, such that the hydrolysate flows through the packed bed and the fiber side of the micro-porous hollow fiber contactor, and the ketose is extracted from the hydrolysate to the immiscible organic phase on the shell side of the micro-porous hollow fiber contactor. 26. The method of claim 1, including: selecting the ABA such that, at selected pH and temperature conditions, the ABA mainly binds to xylulose, and does not bind to any appreciable amounts of glucose, xylose, or fructose. 27. The method of claim 1, including circulating the hydrolysate through at least a first column comprised of a packed bed of immobilized xylose isomerase (XI), and through a vessel having an ABA-enriched phase therein. 28. The method of claim 1, wherein the pH of the recovered ketose is a pH suitable for converting the ketose to ethanol by native S. cerevisiae or other native microorganisms. 29. The method of claim 1, including controlling a volume of the low pH medium sufficient to recover the ketose as a concentrated solution. 30. The method of claim 1, including separating xylose from other C6 sugars as its keto-isomer and allowing for the recovery of xylulose as a concentrated solution. 31. The method of claim 1, comprising passing the isomerized hydrolysate and the ABA containing organic phase through a micro-porous hollow fiber contactor. 32. The method of claim 1, wherein the ABA is selected from the group consisting of PBA, 3aPBA, 4cPBA, naphthalene-2-boronic acid (N2B), and 4-biphenylboronic acid. 33. The method of claim 1, wherein the ABA has the formula Ar—B(OH)2, where Ar represents an unsubstituted or substituted aryl group. 34. The method of claim 33, wherein the ABA comprises one or more of the aryl groups: 4-PhC6H4—; 4-MeC6H4—, where Me is methyl; 2-iPrC6H4-, where iPr is isopropyl; 2-naphthyl; 3-BnOC6H4—, where Bn is benzyl; 4-MeO2CC6H4—, where Me is methyl; and 4-pyridinyl. 35. The method of claim 33, wherein the ABA comprises a diboronic acid that exhibits a higher selectivity toward ketose binding compared to monoboronic acids. 36. The method of claim 33, wherein the ABA comprises a multi-dentate boronic acid carrier. 37. The method of claim 36, wherein the ABA comprises one or more of: wherein A and C are B(OH)2, and B and D are H groups. 38. The method of claim 1, wherein the ABA comprises a hydrophobic substituted aryl boronic acid. 39. The method of claim 38, wherein the ABA comprises: 40. The method of claim 38, wherein the hydrophobic substituted aryl boronic acid is used in a liquid-liquid extraction followed by stripping or micro-porous hollow fiber contactor implementation.
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