WO2010030617A1 - Procédé de récupération d’acide lévulinique - Google Patents

Procédé de récupération d’acide lévulinique Download PDF

Info

Publication number
WO2010030617A1
WO2010030617A1 PCT/US2009/056296 US2009056296W WO2010030617A1 WO 2010030617 A1 WO2010030617 A1 WO 2010030617A1 US 2009056296 W US2009056296 W US 2009056296W WO 2010030617 A1 WO2010030617 A1 WO 2010030617A1
Authority
WO
WIPO (PCT)
Prior art keywords
furfural
formic acid
acid
levulinic acid
materials
Prior art date
Application number
PCT/US2009/056296
Other languages
English (en)
Inventor
Frank Seibert
Original Assignee
Meadwestvaco Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Meadwestvaco Corporation filed Critical Meadwestvaco Corporation
Publication of WO2010030617A1 publication Critical patent/WO2010030617A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment

Definitions

  • Levulinic acid has been recognized in various applications. It is a starting material for the production of a variety of industrial and pharmaceutical compounds such as resins, plasticizers, herbicides, and specialty chemicals. However, its commercial significance has been limited due in part to its high production cost. Several methods have been reported for preparing levulinic acids. However, these synthetic methods often require high-cost raw materials and provide low synthetic yields.
  • U.S. Patent No. 5,608,105 discloses a process of producing levulinic acid and formic acid from carbohydrate-containing raw materials using two reactors in which the temperature, reaction time, and acid content are closely controlled.
  • the raw materials are supplied to a first reactor and hydrolyzed at between 210° C-230° C in the presence of mineral acid to produce hydroxymethylfurfural along with other reaction intermediates, which are then conveyed into a second reactor.
  • the resulting hydroxymethylfurfural is hydrolyzed further at 195° C-215° C in the presence of mineral acid in the second reactor to produce levulinic acid, furfural, formic acid, and other by-products.
  • the process conditions of the second reactor are adjusted such that furfural and formic acid are vaporized and externally condensed, whereas the levulinic acid is concentrated at the bottom of the reactor. Once the concentration of the levulinic acid is sufficiently high, a stream containing levulinic acid is removed from the steady-state reaction mix in the reactor. Since the conditions in the second reactor must facilitate both the hydrolysis reaction and the separation of levulinic acid from other by- products, the optimum condition ranges could be limited and high level of operational preciseness is required for each manufacturing production.
  • U.S. Patent No. 5,859,263 describes a process for producing levulinic acid by extruding a mixture of starch, water and mineral acid in a screw extruder at a temperature of 80°C-150°C. Then, the levulinic acid is isolated from the reaction product mixture by a series of steps: filtration, steam distillation, condensation, and finally centrifugation.
  • U.S. Patent No. 5,892,107 discloses a method of recovering levulinic acid from an aqueous acidic hydrolysis reaction mixture of biomass using chromatography technique. This recovering process demands multiple separation steps and chromatographic columns in order to achieve an acceptable recovery yield.
  • U.S. Patent No. 7,153,996 reports the use of olefin to facilitate the separation of levulinic acid from other reaction products of the acidic hydrolysis of biomass.
  • the biomass is acidic hydrolyzed to provide a mixture of levulinic acid, formic acid and furfural.
  • the aqueous product mixture is reacted with at least one olefin, optionally in the presence of a second acid catalyst, to produce an aqueous phase and an organic phase containing levulinic esters and formic esters.
  • the organic phase is separated from the aqueous phase.
  • the levulinic acid is never isolated from other by- products. Rather, the levulinic acid is converted into levulinic ester and applied for the selected end-used applications as a mixture with formate ester.
  • U.S. Patent No. 7,378,549 teaches a reactive extraction of levulinic acid by contacting an aqueous acidic hydrolysis reaction mixture with liquid esterifying alcohol at esterification conditions in the presence of a catalyst.
  • the liquid esterifying alcohol is substantially water-immiscible and comprises at least four carbon atoms.
  • the extraction conditions and the amount of esterifying alcohol are controlled such that the levulinic acid in the aqueous mixture reacts with the esterifying alcohol solvent to provide levulinate ester, which is then extracted from the aqueous mixture.
  • the isolated levulinic ester must be subjected to yet another acidic hydrolysis reaction to convert the levulinic ester back to the desired levulinic acid.
  • U.S. Patent No. 7,520,905 discloses a method of producing biodiesel fuel via an acidic hydrolysis of biomass using sulfuric acid as catalyst.
  • the acidic hydrolysis of biomass provides sugars, which is then converted into dehydrated sugars, such as furfural and hydroxymethylfurfural (HMF).
  • Sulfuric acid serves as a catalyst for HMF heterocyclic ring opening to form levulinic acid, resulting in a hydrolysate containing furfural, formic acid, and levulinic acid.
  • Biodiesel fuel oil such as soybean oil and canola oil, is used to extract furfural and levulinic acid from the hydrolysis product mixture.
  • the extracted hydrolysate is subjected to a water permeable member to reduce the water content, and subsequently recycled for further hydrolysis of biomass.
  • the sulfuric acid is recovered and reused for the hydrolysis operation.
  • the formic acid, thus formed is unstable and decomposes within hot sulfuric acid to yield water and carbon monoxide. Therefore, a valuable formic acid is lost in the process. Additionally, the carbon monoxide resulted from the decomposition of formic acid leads to environmental concerns of carbon footprints.
  • the product of the disclosed process is biodiesel oil containing a mixture of furfural and levulinic acid as additives; therefore, the disclosed process does not isolate levulinic acid from furfural.
  • a method of recovering levulinic acid from an aqueous mixture containing levulinic acid, formic acid and furfural is disclosed that is simple to operate and economical for commercial scale production.
  • the mixture may be obtained by acidic hydrolysis of various raw materials, including low-cost natural products such as biomass.
  • Furfural one of the products in the aqueous mixture, is used as an extracting solvent.
  • the mixture is separated into an aqueous-rich phase containing some formic acid and furfural; and a furfural-rich phase containing some water, levulinic acid, formic acid and furfural.
  • the levulinic acid may be isolated from the furfural-rich phase through distillation.
  • the furfural- rich phase may be subjected to a series of distillation process to isolate formic acid from the furfural solvent.
  • a fraction of the furfural recovered from the distillation may be recycled and reused as an extracting solvent; the remaining fraction may be sold as product.
  • FIG. 1 is a schematic diagram of a known process for isolating levulinic acid from other reaction products of the acidic hydrolysis of biomass;
  • FIG. 2 is a schematic diagram of one embodiment of the disclosed process for isolating levulinic acid from an aqueous mixture comprising furfural, formic acid, and levulinic acid;
  • FIG. 3 is a graph showing a comparative equilibrium distribution of levulinic acid and formic acid in two different solvents: furfural and water;
  • FIG. 4 is a graph showing the comparative partitioning of levulinic acid for three different solvents: furfural, methyl isobutyl ketone (MIBK), and isopropyl acetate (IPA);
  • FIG. 5 is a schematic diagram of one embodiment of the disclosed process for isolating levulinic acid from an aqueous mixture comprising furfural, formic acid, and levulinic acid;
  • FIG. 6 is a schematic diagram showing a stream analysis for the extraction vessel being fed with furfural extracting solvent and the aqueous condensate comprising furfural, and formic acid;
  • FIG. 7 is a schematic diagram showing a stream analysis for the extraction vessel being fed with furfural extracting solvent and the hydrolysate comprising formic acid, furfural, and levulinic acid;
  • FIG. 8 is a schematic diagram showing a stream analysis for the distillation vessel of a mixture containing furfural, formic acid and levulinic acid;
  • FIG. 9 is a schematic diagram showing a stream analysis for the distillation vessel of a mixture containing furfural, formic acid and water.
  • FIG. 10 is a schematic diagram showing a stream analysis for the distillation vessel of a mixture containing furfural and formic acid and water.
  • FIG. 1 shows a known process of extracting levulinic acid from an aqueous- rich feed using a conventional solvent such as methyl isobutyl ketone (MIK) or isopropyl acetate (IPA).
  • MIK methyl isobutyl ketone
  • IPA isopropyl acetate
  • four distillation columns are used to separate five components: crude levulinic acid, conventional solvent, water, furfural and formic acid.
  • the crude levulinic acid is purified with another distillation column to remove non-volatile impurities.
  • a steam stripper must be utilized to recover the conventional solvent and minimize solvent loss to the aqueous raffmate leaving the extraction.
  • the biomass is hydrolyzed in a presence of a strong acid in the mixer, providing an aqueous acidic hydrolysis mixture comprising levulinic acid along with formic acid and furfural by-products.
  • the resulting aqueous acidic hydrolysis mixture is then flashed to separate out an aqueous condensate (1), comprising formic acid and furfural by-products.
  • the other portion of the aqueous acidic hydrolysis mixture is further hydrolyzed and then concentrated to provide hydrolysate containing levulinic acid along with other acidic hydrolysis by-products.
  • the hydrolysate is subjected to filtration prior to an extraction process.
  • the filtered hydrolysate is then fed into an extraction along with a water-immiscible solvent and the condensate (1).
  • the water- immiscible solvents suitable as extracting solvents are low molecular weight ketones, ethers or acetates, such as those containing more than five carbon atoms.
  • the compounds in the extraction vessel are extracted into (i) an organic phase (extract) containing levulinic acid, formic acid, furfural and the extracting water-immiscible solvent; and (ii) an aqueous phase (raffinate) containing acid catalyst and a small amount of the water-immiscible solvent.
  • the resulting aqueous phase is then subjected to a (steam) stripping column, wherein the water- immiscible solvent is isolated from the aqueous solution.
  • the isolated aqueous portion containing the acid is recycled back to mixer and reused in the acid-hydrolysis reaction.
  • the isolated water-immiscible solvent is recycled back to the extraction vessel and reused as the extracting solvent.
  • the organic phase (extract) is distilled to provide a first bottom stream containing crude levulinic acid and a first overhead stream containing some water, formic acid, furfural, and the extracting solvent.
  • the obtained crude levulinic acid is distilled to provide purified levulinic acid.
  • the first overhead stream containing some water, formic acid, furfural and the extracting solvent is then subjected to further distillation to separate the extracting solvent as a second overhead stream from a second bottom stream containing a mixture of formic acid and furfural.
  • the second bottom stream is finally distilled to separate formic acid from furfural, providing a third overhead stream containing formic acid residues and a third bottom stream containing furfural.
  • FIG. 2 shows one embodiment of the disclosed method of recovering levulinic acid from an aqueous acidic hydrolysis mixture.
  • This embodiment comprises steps of: (a) acidic hydrolysis of a raw material, such as biomass, to produce an aqueous mixture comprising levulinic acid, formic acid, and furfural; (b) flashing the aqueous mixture to provide a condensate portion (1) comprising water, formic acid and furfural; and a hydrolysate portion comprising formic acid, furfural and levulinic acid;
  • the biomass from a refiner may be used as a raw material for the acidic hydrolysis reaction.
  • the biomass is fed into a mixer and hydrolyzed in a presence of an acid catalyst to provide an aqueous acidic hydrolysis mixture comprising levulinic acid, formic acid, and furfural.
  • the mixture may be flashed to separate an aqueous condensate (1), containing formic acid and furfural, from the rest of the mixture.
  • the rest of the mixture is hydrolyzed and, optionally concentrated, to provide a hydrolysate containing levulinic acid, formic acid and furfural.
  • the hydrolysate may be subjected to filtration prior to extraction. Furfural is used as an extracting solvent.
  • the hydrolysate is fed into an extraction vessel along with the condensate (1) and the furfural extracting solvent.
  • the furfural solvent extracts the mixture in a vessel.
  • the furfural-rich phase may be distilled in a first distillation vessel to provide a first bottom stream containing crude levulinic acid, and a first overhead stream containing some water, formic acid and furfural.
  • the first bottom stream may be subjected to further distillation to provide purified levulinic acid.
  • the first overhead stream is fed to a second distillation column where furfural is separated as a bottoms product.
  • the second distillate contains some water, some furfural and formic acid and is fed to a third distillation column. Water and furfural are removed as a light boiling azeotrope and formic acid is removed as a bottoms product.
  • the light boiling water- furfural azeotrope could be removed in the second distillation column and the bottoms of the second distillation column containing furfural and formic acid is fed to the third distillation column.
  • formic acid is distilled as an overhead product and furfural is recovered as a bottoms product. It is to be understood that other alternative processes may be used to isolate furfural and formic acid from the first overhead stream.
  • FIG. 3 shows a comparative equilibrium distribution of levulinic acid and formic acid in two different solvent media: furfural and water.
  • FIG. 4 compares the partitioning of levulinic acid in furfural solvent to two conventional solvents: methyl isobutyl ketone (MIBK) and isopropyl acetate (IPA).
  • MIBK methyl isobutyl ketone
  • IPA isopropyl acetate
  • the extraction selectivity of furfural for levulinic acid may be twice of those for the MIBK and IPA solvents.
  • the required extracting solvent/feed ratio may be reduced by a factor of two.
  • the furfural has superior extraction power, compared to conventional solvents, to pull levulinic acid, formic acid, and of course additional furfural from the aqueous acidic hydrolysis reaction mixture into the organic phase during the extraction process.
  • furfural may be beneficial as an azeotroping solvent in removing water during the recovery of formic acid.
  • the need of azeotroping solvent may be minimized, if not completely eliminated.
  • Drying agent such as molecular sieve may not be required.
  • FIG. 5 shows one embodiment of the disclosed method of recovering levulinic acid from an aqueous acidic hydrolysis mixture.
  • the method comprises steps of: (a) acidic hydrolysis of a raw material, such as biomass, to produce an aqueous mixture comprising levulinic acid, formic acid, and furfural;
  • the disclosed method of recovering levulinic acid from such hydrolysis mixture utilizes the furfural by-product as an extracting solvent.
  • the disclosed method requires no additional extracting solvent, thereby eliminating the raw material cost for extracting solvent and the operation cost for additional separation steps required to isolate the desired chemicals from the extracting solvent itself.
  • the disclosed process is much simpler to operate compared to the processes of known art; therefore, a significant reduction in operation cost may be achieved.
  • the capital cost may be substantially reduced since, comparing to the processes of known art, the disclosed process requires fewer storage tanks and distillation columns.
  • the disclosed process is suitable for recovering levulinic acid for an aqueous acidic hydrolysis reaction mixture of a variety of raw materials.
  • low-cost natural products such as biomass may be used as the raw material source.
  • the sources from biomass include, but are not limited to, rice straw materials, woody plant materials, paper materials, cotton materials, lignocellulosic materials, corn stalks, bagasse, sugar-based materials, carbohydrate materials, and mixtures thereof.
  • Furfural was used as an extracting solvent to isolate levulinic acid and formic acid from an aqueous acidic hydrolysis reaction mixture.
  • the liquid extractions were carried out using a 2.5 cm-diameter Karr reciprocating plate extractor. The extraction was performed at 25° C.
  • the distillation was performed in a 2.8 cm-diameter Oldershaw distillation column containing 40 trays, and the operating pressure was controlled at 0.97 psi (950 mmHg).
  • a thermal conductivity detector gas chromatography (GC) was used to quantify the amount of chemical compounds.
  • FIG. 5 showed one example of the separation processes used in the study.
  • the condensate feed CF-I comprised water and formic acid as shown in TABLE 1.
  • the condensate feed CF-I was fed into the extraction vessel E-I along with the furfural extracting solvent FS-I.
  • the liquid-liquid extraction took place in E-I vessel and separated an aqueous-rich stream R- 1 containing mainly water from a furfural-rich stream EX-I.
  • the aqueous-rich stream R-I could be subjected to a stream stripper (not shown in FIG. 5) to recover furfural and some formic acid residues.
  • the furfural-rich stream EX-I comprising water, formic acid and furfural, was analyzed by GC to quantify the amount of recovered formic acid. As shown in TABLE 1 and FIG. 6, approximately at least 40% of the formic acid was recovered from the E- 1 extraction process.
  • the hydrolysate feed HYFD-2 comprised water, furfural, formic acid, sulfuric acid, levulinic acid and small amount of other unidentified acid as shown in TABLE 2.
  • the hydrolysate feed HYFD-2 was fed into the extraction vessel E-2, along with furfural extracting solvent FS-2.
  • the liquid-liquid extraction separated the aqueous-rich stream R-2 containing mainly water from the furfural-rich stream EX -2 containing furfural, formic acid and levulinic acid.
  • the aqueous-rich stream R-2 was subjected to a stream stripper (not shown in FIG. 5) to recover furfural and some formic acid residues.
  • the furfural-rich stream EX-2 was analyzed by GC to quantify the amount of recovered levulinic acid. As shown in TABLE 2 and FIG. 7, at least 90% of the levulinic acid and 40% or more of formic acid were recovered from the E-2 extraction process.
  • the furfural-rich stream EX-2 was fed to a first vacuum distillation D-I, wherein the levulinic acid was isolated as a bottom stream BOT-I from the overhead stream OVHD-I.
  • the OVHD-I stream was subjected to a stream stripping (not shown in FIG. 5) to provide OVHD-I Light portion and OVHD-I Heavy portion.
  • the compositions of each stream were quantitatively determined using GC analysis. (TABLE 3, FIG. 8).
  • the isolated overhead stream OVHD-I stream and the furfural -rich stream EX-I were fed into a second vacuum distillation D-2.
  • the OVHD-I and EX-I streams could be combined prior to feeding into the distillation vessel D-2.
  • water and furfural formed a low boiling point azeotrope that was isolatable as an overhead stream OVHD-2 from the bottom stream BOT-2 containing formic acid and furfural.
  • the OVHD-2 stream was subjected to a stream stripping (not shown in FIG. 5) to provide OVHD-2 Light portion and OVHD-2 Heavy portion.
  • the compositions of each stream were quantitatively determined using GC analysis. (TABLE 4 and FIG. 9)
  • the bottom stream BOT-2 was then subjected to a third vacuum distillation D- 3 to isolate the formic acid from furfural solvent.
  • the distillation provided the overhead stream OVHD-3 containing formic acid that was isolatable from the bottom stream BOT-3 containing mainly furfural solvent.
  • the recovered furfural solvent in the bottom stream BOT-3 may be recycled back to the extraction vessels E-I and E-2 and reused as the extracting solvents for the condensate and the hydrolysate, respectively.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L’invention concerne un procédé de récupération d’acide lévulinique à partir d’un mélange aqueux contenant de l’acide lévulinique, de l’acide formique et du furfural. Le mélange aqueux peut être obtenu par hydrolyse acide de diverses matières premières, y compris des produits naturels peu coûteux tels que la biomasse. Le furfural, un des produits contenus dans le mélange aqueux, est utilisé en tant que solvant d’extraction. Le mélange est extrait en une phase riche en eau qui contient une certaine quantité d’acide formique et du furfural; et une phase riche en furfural qui contient une certaine quantité d’eau, de l’acide lévulinique, de l’acide formique et du furfural. L’acide lévulinique peut être isolé à partir de la phase riche en furfural par distillation. La phase riche en furfural peut être soumise à une série de procédés de distillation pour isoler l’acide formique du solvant furfural. Une fraction du furfural récupéré à partir de la distillation peut être recyclée et réutilisée en tant que solvant d’extraction; la fraction restante peut être vendue en tant que produit.
PCT/US2009/056296 2008-09-09 2009-09-09 Procédé de récupération d’acide lévulinique WO2010030617A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US9537008P 2008-09-09 2008-09-09
US61/095,370 2008-09-09

Publications (1)

Publication Number Publication Date
WO2010030617A1 true WO2010030617A1 (fr) 2010-03-18

Family

ID=41466816

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2009/056296 WO2010030617A1 (fr) 2008-09-09 2009-09-09 Procédé de récupération d’acide lévulinique

Country Status (1)

Country Link
WO (1) WO2010030617A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2537841A1 (fr) 2011-06-22 2012-12-26 DSM IP Assets B.V. Production en continu de furfural et dýacide lévulinique
WO2013090041A1 (fr) * 2011-12-15 2013-06-20 Wisconsin Alumni Research Foundation Production accrue à l'aide de solutés de gamma-valérolactone (gvl) à partir de solutions aqueuses d'acide lévulinique
WO2014087015A1 (fr) * 2012-12-07 2014-06-12 Dsm Ip Assets B.V. Procédé pour isoler de l'acide lévulinique et de l'acide formique
WO2014087016A1 (fr) * 2012-12-07 2014-06-12 Dsm Ip Assets B.V. Procédé pour la production d'un hydrolysat de biomasse
US9073841B2 (en) 2012-11-05 2015-07-07 Segetis, Inc. Process to prepare levulinic acid
WO2015134352A1 (fr) * 2014-03-03 2015-09-11 Segetis, Inc. Procédé d'élimination d'acide minéral à partir d'acide lévulinique
EP3115351A1 (fr) 2015-07-10 2017-01-11 GFBiochemicals Ltd. Compositions d'acide lévulinique
EP3115353A1 (fr) 2015-07-10 2017-01-11 GFBiochemicals Ltd. Procédé d'isolation d'acide lévulinique
EP3115352A1 (fr) 2015-07-10 2017-01-11 GFBiochemicals Ltd. Procédé d'isolation d'acide lévulinique
EP3156389A1 (fr) 2015-10-12 2017-04-19 GFBiochemicals Ltd Procédé de purification de l'acide lévulinique
WO2018011741A1 (fr) * 2016-07-15 2018-01-18 Sabic Global Technologies B.V. Synthèse de cétals et de lévulinates
US10618864B2 (en) 2011-11-23 2020-04-14 Gfbiochemicals Ip Assets B.V. Process to prepare levulinic acid
CN112607939A (zh) * 2020-12-01 2021-04-06 维讯化工（南京）有限公司 利用连续萃取法回收氰氟草酯溶剂的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2684982A (en) * 1951-11-19 1954-07-27 Quaker Oats Co Recovery of levulinic acid
EP0012321A1 (fr) * 1978-12-14 1980-06-25 BASF Aktiengesellschaft Procédé pour l'obtention d'acide formique anhydre ou pratiquement anhydre

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2684982A (en) * 1951-11-19 1954-07-27 Quaker Oats Co Recovery of levulinic acid
EP0012321A1 (fr) * 1978-12-14 1980-06-25 BASF Aktiengesellschaft Procédé pour l'obtention d'acide formique anhydre ou pratiquement anhydre

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2537841A1 (fr) 2011-06-22 2012-12-26 DSM IP Assets B.V. Production en continu de furfural et dýacide lévulinique
US8426619B2 (en) 2011-06-22 2013-04-23 Dsm Ip Assets B.V. Continuous production of furfural and levulininc acid
US10618864B2 (en) 2011-11-23 2020-04-14 Gfbiochemicals Ip Assets B.V. Process to prepare levulinic acid
WO2013090041A1 (fr) * 2011-12-15 2013-06-20 Wisconsin Alumni Research Foundation Production accrue à l'aide de solutés de gamma-valérolactone (gvl) à partir de solutions aqueuses d'acide lévulinique
US9598341B2 (en) 2012-11-05 2017-03-21 Gfbiochemicals Limited Process to prepare levulinic acid
US9073841B2 (en) 2012-11-05 2015-07-07 Segetis, Inc. Process to prepare levulinic acid
CN104854075A (zh) * 2012-12-07 2015-08-19 帝斯曼知识产权资产管理有限公司 分离乙酰丙酸和甲酸的方法
WO2014087016A1 (fr) * 2012-12-07 2014-06-12 Dsm Ip Assets B.V. Procédé pour la production d'un hydrolysat de biomasse
WO2014087015A1 (fr) * 2012-12-07 2014-06-12 Dsm Ip Assets B.V. Procédé pour isoler de l'acide lévulinique et de l'acide formique
US9908836B2 (en) 2012-12-07 2018-03-06 Georgia-Pacific LLC Process for the isolation of levulinic acid and formic acid
WO2015134352A1 (fr) * 2014-03-03 2015-09-11 Segetis, Inc. Procédé d'élimination d'acide minéral à partir d'acide lévulinique
US9944584B2 (en) 2014-03-03 2018-04-17 Gfbiochemicals Limited Method for removing mineral acid from levulinic acid
US10369492B2 (en) 2015-07-10 2019-08-06 Gfbiochemicals Ip Assets B.V. Process for the isolation of levulinic acid
WO2017009211A1 (fr) 2015-07-10 2017-01-19 GFBiochemicals Ltd. Procédé permettant l'isolement de l'acide lévulinique
EP3115352A1 (fr) 2015-07-10 2017-01-11 GFBiochemicals Ltd. Procédé d'isolation d'acide lévulinique
EP3115353A1 (fr) 2015-07-10 2017-01-11 GFBiochemicals Ltd. Procédé d'isolation d'acide lévulinique
US10550067B2 (en) 2015-07-10 2020-02-04 Gfbiochemicals Ip Assets B.V. Levulinic acid compositions
EP3115351A1 (fr) 2015-07-10 2017-01-11 GFBiochemicals Ltd. Compositions d'acide lévulinique
US10702792B2 (en) 2015-07-10 2020-07-07 Gfbiochemicals Ip Assets B.V. Process for the isolation of levulinic acid
EP3156389A1 (fr) 2015-10-12 2017-04-19 GFBiochemicals Ltd Procédé de purification de l'acide lévulinique
WO2017064069A1 (fr) 2015-10-12 2017-04-20 Gfbiochemicals Ltd Procédé pour la purification de l'acide lévulinique
US10239814B2 (en) 2015-10-12 2019-03-26 Gfbiochemicals Ip Assets B.V. Process for the purification of levulinic acid
WO2018011741A1 (fr) * 2016-07-15 2018-01-18 Sabic Global Technologies B.V. Synthèse de cétals et de lévulinates
CN112607939A (zh) * 2020-12-01 2021-04-06 维讯化工（南京）有限公司 利用连续萃取法回收氰氟草酯溶剂的方法
CN112607939B (zh) * 2020-12-01 2022-09-09 维讯化工（南京）有限公司 利用连续萃取法回收氰氟草酯溶剂的方法

Similar Documents

Publication Publication Date Title
WO2010030617A1 (fr) Procédé de récupération d’acide lévulinique
Kiss et al. Separation technology–Making a difference in biorefineries
CA2721165C (fr) Procede de recuperation d'acide formique
DK2872495T3 (en) METHOD OF PRODUCING furfural and levulinic OF lignocellulosic biomass
US8901325B2 (en) Method for producing furfural from lignocellulosic biomass material
CA2765760C (fr) Procede de production d'alcool
US9656940B2 (en) Process for the recovery of acetic acid
US20100312006A1 (en) Production of levulinic acid and levulinate esters from biomass
WO2011161141A1 (fr) Procédé de séparation du furfural à partir d'une phase aqueuse liquide contenant du furfural et un ou plusieurs acides organiques
WO2012041990A1 (fr) Procédé d'obtention de furfural
US9790523B2 (en) Energy efficient batch recycle method for the production of biomolecules
CN111689842A (zh) 一种节能环保的从纤维素材料生产目标化学化合物的方法
CA3039790A1 (fr) Procede de recuperation de furfural
EP1594834A1 (fr) Procede pour obtenir des esters d'alkyle d'acide gras, des acides resiniques et des sterols a partir de tall oil brut
JP2017506083A (ja) フルフラールの製造方法
CN106397183B (zh) 从生物质酸催化水解产物中分离乙酰丙酸、甲酸和糠醛的方法
US10584107B2 (en) Process for the recovery of furfural
EP2648818A1 (fr) Procédé pour la récupération d'acide organique à partir d'une solution aqueuse diluée
CA3039792A1 (fr) Procede de recuperation de furfural
CN109890800B (zh) 用于回收糠醛的工艺
US9944584B2 (en) Method for removing mineral acid from levulinic acid
CN113717051A (zh) 一种乙酸丁酯的制备方法
SU910587A1 (ru) Способ выделени уксусной кислоты из водных растворов гомологов
WO2015170082A1 (fr) Procédé de récupération d'acide

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09792342

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09792342

Country of ref document: EP

Kind code of ref document: A1