CN105378092A - Process for making furfural - Google Patents
Process for making furfural Download PDFInfo
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- CN105378092A CN105378092A CN201580001288.7A CN201580001288A CN105378092A CN 105378092 A CN105378092 A CN 105378092A CN 201580001288 A CN201580001288 A CN 201580001288A CN 105378092 A CN105378092 A CN 105378092A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
- C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D307/08—Preparation of tetrahydrofuran
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
- C12P17/02—Oxygen as only ring hetero atoms
- C12P17/04—Oxygen as only ring hetero atoms containing a five-membered hetero ring, e.g. griseofulvin, vitamin C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
Processes are described for producing furfural from a mixture of pentoses and hexoses, by dehydrating and cyclizing pentoses to provide furfural using a water-soluble acid at elevated temperatures in the presence of a low-boiling, water-immiscible organic solvent, such as toluene, which is effective for extracting the furfural into an organic phase portion. In certain embodiments, a fermentation step occurs prior to the dehydration step to convert hexoses in the mixed pentoses and hexoses to ethanol while conserving pentoses therein for making furfural.
Description
Background
Biomass (its carbon content is the material of biogenetic derivation instead of fossil sources) are utilized to provide at present derived from chemical and the fuel product of the material (as oil) of fossil sources, or acceptable bio-based, the functional replacement to this kind of chemical and fuel product is provided, day by day become the focus of Recent study and development investment and effort, because the supply of the material of fossil sources has been subjected to and has jeopardized or to its acquisition and to use be more difficult or costliness.
The substitute of some chemical and fuel product or substitute are produced with large commercial scale from biomass.Such as, for liquid feul field, produce ethanol and biofuel (fatty acid alkyl ester class) from corn or other cereal and from sugarcane (for ethanol) and from each vegetable oil and fat (for biofuel) with commercial scale up to now.
But, people recognize for a long time can produce suitable liquid fuel and fuel dope will be preferred from lignocellulose biomass, these lignocellulose biomass contain the xylogen (with dry weight basis) being insoluble to acid detergent of typically 6% or more and are not used as foodstuff products, or these lignocellulose biomass can significantly adversely affects in Land-Use and behavior (such as, deforestation comes soybean outside delivery capacity, corn or similar crop) situation harvesting or buying and use.Many non-food lignocellulose biomass with this feature can be considered, comprise, such as, the non-food biomass crops (as grass, sweet sorghum, fast-growing tree) having object to cultivate, or more particularly, timber refuse (as beta pruning, wood chip, sawdust) and green waste (such as leaf, grass bits, vegetables and fruit waste).In addition according to estimates, with regard to for food crops or other objects the soil cultivated with regard to, about 3/4ths of the biomass produced are refuses, so no matter in question biomass are (for these crops a kind of food crops or certain other crops, during soil has been dropped in and has cultivated) production in refuse, or cultivate the irrelevant source of crop from any, when obtainable abundant lignocellulosic material, seem that we need can start with lignocellulose biomass the various chemical that manufactures and fuel product in fact should be able to be economically fabricated.
As an actual thing, but, produce from lignocellulose biomass the various chemical paid close attention to and fuel product has many important challenges.First difficulty comes from the very different feature of the various components comprising lignocellulose biomass.
In this, as fossil substrate matter as oil, by required scale and with required quality, economy and efficiency produce need maybe by the reality of the omnibearing commercial chemicals needed and fuel product substitute or substitute, the ability of real world is somewhat dependent upon raw material (lignocellulose biomass) how can by effectively and be fractionated into its integral part efficiently, and these integral parts how about can by effectively and efficiently further processing produce desired commercial chemicals and fuel product substitute or substitute.
Lignocellulose biomass is formed primarily of Mierocrystalline cellulose, hemicellulose and lignin portion, and wherein Mierocrystalline cellulose is maximum in these three kinds of components.Cellulose-derived from the structure organization of plant, and is made up of the long-chain of the β glucoside residue be connected by Isosorbide-5-Nitrae position.These connections make Mierocrystalline cellulose have high crystallinity, and therefore have low accessibility to following enzyme or acid catalyst, that is: these enzymes or acid catalyst have been proposed to be used in and this cellulose hydrolysis is become C
6sugar (or hexose) is for further processing.By contrast, hemicellulose is a kind of non-crystalline state heteropolymer being easy to be hydrolyzed, and xylogen (a kind of aromatic series three-dimensional polymer) is dispersed among Mierocrystalline cellulose in plant fiber cells and hemicellulose and proposed for the most important challenge of processing further and upgrade.
Due to the Mierocrystalline cellulose of biomass, difference between hemicellulose and lignin portion, consider equally in various biomass with other the less parts existed in various degree, as the U.S. Patent number 5 of Farone etc., 562, involved by 777 " utilizing the strong acid hydrolysis of Mierocrystalline cellulose and hemicellulose material to produce the method (MethodofProducingSugarsUsingStrongAcidHydrolysisofCellul osicandHemicellulosicMaterials) of carbohydrate ", develop or be proposed many methods for many years carry out fractionating lignocellulosic biomass and be hydrolyzed to Mierocrystalline cellulose and hemicellulose fraction.
Basically, biological and abiotic two kinds of methods are disclosed, wherein the most ancient and foremostly produce the non-biological methods of carbohydrate from Mierocrystalline cellulose and relate to acid hydrolysis, the most generally use the hydrolysis based on sulfuric acid of diluted acid approach, concentrated acid approach or both combinations.' 777 patents of the people such as Farone describe the merits and demerits of this area multiple method based on sulfuric acid known subsequently, and propose a further variant, this variant uses strong acid/sulphuric acid hydrolysis effect and uses repeatedly the step combination of decrystallizing of one or many, wherein biomass (and/or comprising the solid substance stayed from once previously repeatedly interior step of decrystallizing) mix with the biomass of a solubilising part with 25-90% sulphuric acid soln, subsequently this acid is diluted between 20% and 30%, and mixture is preferably heated to 80 and and continue for some time between 100 degrees Celsius with the still unhydrolysed cellulosic sections of solubilising and any hemicellulose material.
Recently, in the some applications jointly transferred the possession of with the application, we have described for fractionating lignocellulosic biomass and one or more then further in processing of cellulose, half fiber and lignin portion to produce the various alternative method having the product of commercial significance.
Such as, in the US2013/013331 (" US ' 331 ") of the people such as Binder, describe a kind of method, wherein preferably near the bleeding point of biomass, under the condition of the hemicellulose material depolymerization being enough to make in biomass and xylogen solubilising, one first, weak organic acid are applied to lignocellulose biomass.Then by dry for the biomass of the acidifying through " boiling " so that from wherein removing moisture to a certain degree, thus can by the solids granulated of this drying to be transported to a central facilities.Then; at this central facilities place; by granulation, through weak acid processing biomass with a kind of solvent or solvent mixture washing; this solvent or solvent mixture can effectively by being separated with the hemicellulose of depolymerization and xylogen of dissolving from the cellulosic sections of these biomass; and be then applicable under the condition that a kind of hexose product or stream are provided, this cellulosic sections is contacted with one second, strong inorganic acid (or multiple acid).Preferably, at elevated temperatures, with the form of steam by this first, weak organic acid is applied to biomass, this is in order to the drying load before reducing granulation step in part.
In US2014/322766 (" US ' 766 "), US2014/022742 (" US ' 742 ") and US2014/0322763 (" US ' 763 "); describe for processing lignocellulose biomass to form a kind of method of acylated cellulose paper pulp and the improvement for the method, the method comprises the C of group under being selected from making a kind of lignocellulose biomass and the first amount
1-C
2acid contact, this group is made up of the following: acetic acid, formic acid with and composition thereof.The lignocellulose biomass that this process contacts be heated to a temperature and continue to be enough to the hydrolysis release hemicellulose of first part and for some time of xylogen, forming a kind of hydrolysate liquor and a kind of acidylate lignocellulose filter cake.This acidylate lignocellulose filter cake is separated with this first hydrolysate liquor, and makes this C of itself and the second amount
1-C
2acid contact, to wash off hemicellulose and xylogen from this acidylate lignocellulose filter cake.The acid elution liquid this being comprised solvable hemicellulose and xylogen is separated with this filter cake through acid elution, and makes a kind of C of this filter cake and the first amount
1-C
2the mixable organic solvent exposure of acid, with by this C
1-C
2acid, hemicellulose and xylogen are washed off further from this acidylate filter cake through acid elution, leave a kind of acylated cellulose paper pulp, by itself and this C
1-C
2the mixable solvent wash liquid separation of acid.In another embodiment, this solvent wash liquid and this hydrolysate can be made to merge with at least one in this acid elution liquid, thus form a kind of acidic organic solvent extract.This acidic organic solvent extract is concentrated, forms a kind of acidic organic solvent syrup being enriched with hemicellulose and xylogen.This C of the second amount can be added in that syrup
1-C
2the mixable organic solvent of acid, this second amount is enough to form a kind of throw out be made up of hemicellulose and xylogen.Then this hemicellulose is separated with this acidic organic solvent syrup with the throw out of xylogen.This throw out is mixed with a kind of aqueous solvent, to form a kind of solution of hemicellulose of dissolving and insoluble xylogen, and this insoluble xylogen is separated with the hemicellulose of this dissolving.
" C cited above
1-C
2the mixable organic solvent of acid " be defined as miscible with acetic acid in WO ' 042 and the sedimentary nonacid organic solvent of hemicellulose and xylogen can be formed by a kind of acetic acid solution comprising hemicellulose and xylogen, its condition is only this C
1-C
2the mixable organic solvent of acid is not a kind of halogenated solvent.The organic solvent used has following characteristics: the solubleness of sugar in this solvent must be low, and the subfraction of at least one xylogen must partly dissolve in this solvent.This kind solvent is slight polarity.Preferably, the solubleness of water in this organic solvent should be low.In addition, the polarity of this solvent should not be too low to such an extent as to effectively can not extract acetic acid from water.The example be applicable to comprises low-molecular-weight alcohol, ketone and ester, as C
1-C
4alcohol, acetone, ethyl acetate, methyl acetate and methyl ethyl ketone and tetrahydrofuran (THF).
In the improvement for method described above, in some step, use liquid/liquid separating method to replace filtering, make to avoid viscosity restriction intrinsic in filtration procedure.In this, because by evaporative removal C
1-C
2the mixable organic solvent of acid, the solid in concentrated hemicellulose and xylogen syrup is limited to and is not more than about 40% (owing to filtering relevant viscosity worry).By using liquid/liquid separating method, can carry out evaporating until the concentration of solid in concentrated hemicellulose and xylogen syrup that reaches at least 52%.The solids concn of higher level and then allow acid comparatively in a small amount and solvent to be used in purification step subsequently.Equally, water wash step is needed to the water yield reduced in fact, make acid and the recovery of solvent, the especially water cost reduction be separated with acid mixture.Furthermore describe other optimize and improve.
Summary of the invention
Following present simplification of the present invention general introduction to provide the basic comprehension of some in its aspect.This general introduction is not summary widely of the present invention and it is neither intended to determine that key of the present invention or epochmaking element are not intended to describe its scope yet.This sole purpose summarized is that the prelude using a kind of form of simplification as the more detailed description presented after a while presents concepts more of the present invention.
As described in, no matter for lignocellulose biomass fractionation be what method, the common purpose of these class methods all is to provide the multiple renewable raw materials in enough purity to escalate into further at present derived from chemical and the fuel product of the material (as oil) of fossil sources in a kind of mode of economy, or acceptable bio-based, the functional replacement of these chemical and fuel product.
Usually, seek the syrup being rich in pentose and hexose, such as, as in disclosed US ' 742, US ' 763 and US ' 766 application.These hexoses are easy to be fermented into ethanol, but pentose is then really not so.Therefore, a kind of method of prior art has been the C carrying out mixing
5/ C
6the improvement of the fermentation of sugar stream, recognize even according to the most effective means of hydrolysis ground fractionating lignocellulosic biomass, the pentose of some content will to be present in any hexose product/raw material and the hexose of some content will be present in any pentose product/raw material.
For this consideration, in an aspect, the present invention relates to a kind of for the C of fundamentally different mode process from the mixing of lignocellulose biomass
5/ C
6the method of sugar, and do not need the fermentation process of the long-term practice deviated from for the production of ethanol.At all, instead of attempting to adapt to pentose completely containing the fermentation of hexose starting material with the existence under the background of producing ethanol, initially carrying out a kind of C of mixing
5/ C
6the normal fermentation of the hexose in glycogen material, object is converted into sugar alcohol by minimal for pentose.
According in an embodiment of this first aspect, before this zymohexose step, replenish the C of this mixing with the starch of liquefaction
5/ C
6hexose in glycogen material to provide the Energy harvesting of the improvement in distilation steps subsequently, wherein by C that a kind of alcohol product of commercial grade mixes with at this
5/ C
6pentose in glycogen material and any unconverted hexose are wherein separated.Preferably, again, in this fermentation step, the C being present in this mixing is sought
5/ C
6the minimal conversion of the pentose in glycogen material, makes these carry out forward for further processing after the distillation.Then the C of this mixing
5/ C
6residuum in glycogen material stands acid catalyzed dehydration and cyclisation to produce furfural from these pentoses.In certain embodiments, this dehydration and cyclisation use a kind of water soluble acid at lower boiling, immiscible organic solvent completes under existing with water substantially.By furfural extraction to comprise this lower boiling, substantially with water the organic solvent of immiscible organic solvent mutually in, in an aqueous phase, wherein reclaim unconverted hexose and/or valuable hexose dehydrating prods (such as, 5-(methylol) furfural (or HMF) and levulinic acid).High initial drying solid concentration can be reached in certain embodiments, have with from a kind of C mixed
5/ C
6the much the same quantitative yield of furfural of the pentose in glycogen material and the high accountability of sugar in a kind of biomass of combination.
In certain embodiments, the C of the mixing be fermented
5/ C
6glycogen material is derived from a kind of upstream biomass fractionating method, and wherein a kind of cellulosic component of these biomass is hydrolyzed into hexose and a kind of hemi-cellulose components of these biomass is hydrolyzed into pentose.In the particular embodiment, be used to according to the upstream biomass fractionating method of any one in US ' 742, US ' 763, US ' 766 or US ' 331 application the C generating this mixing
5/ C
6sugar stream.In other embodiments, the C of the mixing be fermented
5/ C
6glycogen material is not derived from the preceding biomass fractionating method of one, but the direct hydrolysis product of whole biomass.
In an alternative embodiment, make from zymohexose step ethanol be combined from an independent amylaceous fermented ethanol, to provide the Energy harvesting of the improvement in distilation steps subsequently, wherein by C that a kind of alcohol product of commercial grade mixes with at this
5/ C
6pentose in glycogen material and any unconverted hexose are wherein separated.
According in another alternate embodiment of this first aspect, before this zymohexose step, the starch that need not liquefy replenishes the C of this mixing
5/ C
6hexose in glycogen material, and the ethanol from this zymohexose step be not recovered in a distilation steps subsequently but on the contrary for change in certain embodiments for the lower boiling in acid catalyzed dehydrating step, substantially with water immiscible organic solvent characteristic and improve the recovery of the valuable hexose dehydrating prods (that is, 5 hydroxymethyl furfural (HMF) and levulinic acid) in this aqueous phase.
In yet another aspect, the present invention relates to a kind of for the C from the mixing from lignocellulose biomass
5/ C
6glycogen material manufactures the method for furfural under a preceding zymohexose step not existing.This substitute in, use the C that a kind of water soluble acid makes this mix at lower boiling, substantially organic solvent immiscible with water under existing
5/ C
6glycogen material stands acid catalyzed dehydration pentose is wherein converted into furfural.By this furfural extraction to an organic solvent mutually in, wherein the valuable hexose dehydrating prods (such as, 5-(methylol) furfural (or HMF) and levulinic acid) in an aqueous phase is reclaimed together with any unconverted hexose.In the particular embodiment, be used to according to the upstream biomass fractionating method of any one in US ' 742, US ' 763, US ' 766 or US ' 331 application the C generating this mixing
5/ C
6sugar stream.In other embodiments, the C of this mixing
5/ C
6glycogen material is not derived from the preceding biomass fractionating method of one, but the direct hydrolysis product of whole biomass.
According in some embodiment in any one, wherein use or do not use zymohexose step, in multiple tandem reactor, complete this acid catalyzed dehydration, wherein add a kind of lower boiling, the substantially immiscible organic solvent with water in the upstream of each reactor of this series connection.In optimizing in order to the another kind reduced for retrieving to design from the energy requirement of the solvent of this furfural dehydrating prods, after the end of this series connection is separated this aqueous fractions and organic moiety, before distilation steps in a part for this organic solvent of head space (overhead) flash distillation to reclaim furfural from this organic moiety.In an alternative method, this organic moiety catalyzed ground decarbonylation is to be converted into furans by furfural, as at our patent cooperation treaty application sequence number PCT/US2014/048783, " method (ProcessforProducingFuranfromFurfuralfromBiomass) for the always furfural production furans of authigenic material " submitted on July 31st, 2014 and require on August 9th, 2013 submit to from U.S. Provisional Patent Application sequence number 61/864, the right of priority of 228 (following " WO ' 783 "), middle description, and then by this furans product of fractionation by distillation and this solvent.
Brief Description Of Drawings
Fig. 1 according to a schematic diagram of this first aspect " whole biomass " method, wherein from the C of the mixing of the hydrolysis of whole biomass
5/ C
6the C using a kind of water soluble acid to make this mix at lower boiling, substantially organic solvent immiscible with water under existing is led in the fermentation of glycogen material
5/ C
6pentose in glycogen material is converted into the acid catalyzed dehydration of furfural.
Fig. 2 is the schematic diagram of an embodiment of method for completing this acid catalyzed dehydration.
The detailed description of illustrative examples
Forward Fig. 1 to now, according to of the present invention a kind of method that a first aspect schematically illustrates, wherein at a kind of C of mixing
5/ C
6hexose in glycogen material is fermented into the C that ethanol makes in this mixing simultaneously
5/ C
6pentose in glycogen material stands acid catalyzed dehydration and cyclisation to produce furfural.
As the summary of " whole biomass " embodiment 10 shown in Figure 1, lignocellulose biomass 12 and a kind of water soluble acid 14 are combined in a digestive organ 16, wherein add steam 18 to provide the heat of these biomass 12 of digestion.Corn grain fiber a kind ofly in the wet wheeling machine of current corn to ethanol, is easy to obtainable biomass, because herein is provided one lignocellulose biomass 12 easily.Preferred water soluble acid 14 for whole biomass method has been used for producing those of furfural from corn cob and analogue in history by being, such as solvable mineral acid is as sulfuric acid, phosphoric acid and hydrochloric acid; At the C of a kind of mixing of use described below
5/ C
6in the alternate embodiment of glycogen material work, this C
5/ C
6glycogen material is from the aforesaid fractionating method relating to an acid hydrolysis step, be these preferred water soluble acids can be maybe can comprise Already in from those in the water-based sugar soln of preceding fractionating method by what understand, and what understand further be that existing acid can be enough to produce furfural from pentose and produce levulinic acid from hexose another optional embodiment.Therefore, such as, these water soluble acids can be maybe to comprise the C being selected from lower group
1-C
2acid, this group is made up of the following: acetic acid, formic acid and their mixture.Other acid catalysts can also be used, such as AlCl
3hexahydrate and hydrochloric acid.Certainly, will be appreciated that and can be used for the acid that should add equally for forming furfural from pentose and being further used for producing levulinic acid from hexose.
Then biomass hydrolysate 20 (or the C of a kind of heat from aforementioned fractionating method mixing of in the future self-digestion device 16
5/ C
6glycogen material) advance in a flasher 22, wherein at head space to flow 24 flashed water gagings.When a kind of hydrolysate stream 26 dewatered enter the making beating (mashing) of the method 10, saccharification and fermentation section time, the hydrolysate stream 26 then this dewatered cools to remove the waste heat of the digestion of the biomass 12 be used in this digestive organ 16.
Then this stream 26 enters in a container 28, wherein using a kind of alkali 30 of interpolation (such as, ammonium hydroxide) partly neutralize and add cellulase 32 (such as, α-amylase enzyme) after, produce a kind of slurry (mash) 34 comprising the mixture of pentose and hexose and the liquefaction of oligopolymer and some non-fermentable solids.Then the slurry 34 of this liquefaction is made to advance in a fermenting container 36, wherein make this slurry 34 according to the alcohol fermentation method of routine and a kind of fermentable, microorganism 38 of producing ethanol (such as, one Yeasts is as yeast saccharomyces cerevisiae, bacterium or fungi) and additional enzyme 40 (such as, glucoamylase) combine to produce ethanol from this slurry 34.Control this fermentation to obtain the minimal conversion of the pentose in this slurry 34 to sugar alcohol, make these pentoses can be converted into furfural subsequently; Such as, under the background of the fermentation by saccharomyces cerevisiae of routine, we have found that this object can obtain in the following manner, follow the trail of the speed that passing carbonic acid gas in time produces, and when this carbonic acid gas generation speed close to zero time and stop this fermentation when the hexose more easily fermented in this slurry 34 exhausts.Be contemplated that likely should transform at least 99.5% in this and preferably up to 99.9% the hexose in initial sugar mixture, and do not have pentose to lose excessive risk, otherwise these pentoses will can be used for the product changing into furfural and can be made up of furfural.Preferably, under any circumstance, control this fermentation, make the pentose of at least 90% keep unconverted however more preferably at least 95% pentose keep unconverted, still more preferably at least 99% pentose keep unconverted and most preferably at least 99.5% pentose keep unconverted.
When suitably and when wishing the more economical recovery being realized the ethanol produced in this way by the reboiler reduced wherein in distillation subsequently, hexose (other the suitable adjustments with the condition of the fermentation in the adjustment of any necessity of the amount and type that flow the enzyme of 40 interpolations and container 36) in this slurry 34 can be replenished by stream 42 by adding the starch liquefied.In other embodiments, the ethanol itself produced in container 36 or when with from other fermentor tanks (no matter the method for parallel connection 10 or operate from other) ethanol in conjunction with time enough to be distilled under the ethanol produced in the starch from added liquefaction economically not existing, add starch by flowing 42 to fermentor tank 36 to omit.
In the embodiment of going back other, as mentioned in above general introduction, the ethanol produced in container 36 using not by distillation as a kind of commercial grades be recovered but by be used to change be used in certain embodiments producing subsequently lower boiling in the acid catalyzed dehydrating step in furfural, substantially with water immiscible organic solvent characteristic and improve except furfural, that is, the recovery of the valuable hexose dehydrating prods outside 5 hydroxymethyl furfural (HMF) and levulinic acid.
But, when wherein to reclaim ethanol of commercial grade product be desired, then by comprising a large amount of ethanol, be used for producing subsequently the pentose of furfural and some non-ly can the product 44 from this fermentor tank 36 of fermentation solid be sent in a distillation column 46.The distillation of this product 44 wherein provides ethanol of commercial grade product (typically and preferably the ethanol of 95%) at head space as stream 48, the appointment comprising dissolving is sent in solid-liquid separation for the production of the pentose of furfural and the bottoms 50 of Fei Ke fermentation solid, such as centrifuge separator 52 simultaneously.Can the solid 54 of in the future self-separation device 52 dry to provide the animal food prods 58 of high protein in a moisture eliminator 56, the pentose of the dissolving from bottoms 50 is recycled in the production stage 62 subsequently for the production of furfural product 64 with liquid starting material 60 from separator 52 simultaneously.
Forward Fig. 2 to now, provide a kind of schematic diagram of such process 62, wherein in the reactor of multiple series connection, acid dehydration comprises the liquid starting material 60 of the pentose of dissolving, wherein adds a kind of lower boiling, the substantially immiscible organic solvent with water in the upstream of each reactor of this series connection.Shown in figure 2 in specific embodiment, pentose continuously completes to the acid dehydration of furfural in three reactor grades (reactorstage) 66 of series connection.In three of the upstream of these reactor grades 66 corresponding increments (increment) 68, add a kind of lower boiling, the substantially immiscible organic solvent with water, on its center line, static mixer 70 is used to mix up hill and dale this solvent and this liquid starting material 60 and the first and second reactor grades 66 after, is used to mix up hill and dale the liquid starting material of this solvent and this Partial Conversion in the upstream of this first reactor grade 66.Preferred lower boiling, immiscible solvent comprises toluene, ethanol, tetrahydrofuran (THF) and methyltetrahydrofuran with water substantially; When manufacturing furans about use furfural and consider from furans to manufacture THF subsequently, toluene and tetrahydrofuran (THF) provide the option obviously integrated, and ethanol can by the C from the fractionation of a kind of aforementioned biological matter or the mixing from the hydrolysis of whole biomass (such as, corn grain fiber) as described in this
5/ C
6hexose in glycogen material produces and because herein is provided additional obvious integration option and benefit.
Stage separation device 72 between reactor grade 66 works to reclaim the organic fraction 74 comprising furfural separately, this furfural passes through at this lower boiling, substantially the dehydration with water in immiscible organic solvent under (and/or comprising in acid-hydrolyzed biomass fractionating method in one in the past) existence of solvable acid catalyst of being added by stream 14 is formed, simultaneously by the sugar of any unconverted five and six carbon, salt, and water-soluble acid catalyst, the aqueous portion 76 that 5 hydroxymethyl furfural and levulinic acid are formed proceeds to the liquid starting material 60 that maybe can be recycled for the beginning with the series at reactor grade 66 in a level 66 subsequently and is combined for being dehydrated into levulinic acid product further.Be separated with the aqueous phase substance 78 of any remnants by the organic fraction 74 collected from some stage separation devices 72 in a decanting vessel 80, wherein furfural/the solvent mixture 82 of institute's decant marches in a flasher 84 to flash off a part 86 for this solvent for recirculation in solvent recycled stream 88.Residuum 90 is distilled to remove for the lower boiling of recirculation in this solvent recycled stream 88, substantially immiscible solvent and this furfural product flow 64 with water in a distillation column 92.
(not shown) in an alternative embodiment, furfural/solvent mixture 82 catalyzed ground decarbonylation of institute's decant so that furfural is converted into furans, as what describe in applying at our WO ' 783.In this application, the 5% furfural raw material synthesized in toluene and the toluene extract containing the acid catalyzed dehydration/cyclisation furfural product of pentose moiety carrying out authigenic material carry out decarbonylation, 1%Pd/Al is used for synthesis material example
2o
3catalyzer and 2%Pd/C catalyzer use identical palladium catalyst on alumina under 250 degrees Celsius under the temperature of scope from 200 degrees Celsius to 250 degrees Celsius and for the dehydration raw material of reality.Other catalyzer can also be used, comprise load with promote or the platinum, rhodium, palladium and the nickel catalyzator that do not promote.Then furans decarbonylation product and solvent is separated by simple distillation.In this, in view of furfural has the boiling point (compared with the boiling point of toluene 110.6 DEG C) of 161.7 degrees Celsius, furans has the much lower boiling point of 31.3 degrees Celsius and therefore can be separated with toluene, wherein needs significantly less energy.
Then can will in this way preparation and reclaim furans hydrogenation to produce tetrahydrofuran (THF) (THF), Yi Zhong
elastomer polyurethane fiber and the important solvent in other polymer production and intermediate.Known multiple catalysts and method are used for this object.Such as, the US2 of the people such as Banford, 846,449 define pure state or the nickel of fine dispersion on a kind of inert support, platinum or palladium, wherein porous or
the reduced nickel of nickel sponge metal catalyst and fine dispersion or diatomite are listed in preferred catalyst choice.
Routinely, manufactured THF from Nonrenewable resources, although carried out over several years about make to find in biomass or become furfural from the dehydration of pentoses that biomass obtain, make this decarbonylation of furfural become furans and then the most at last this furans be hydrogenated to the large quantifier elimination of THF.
But, as one of the largest production business and developer by THF technology a series of relevant file confirm, such as, see, US2013/0168227, US2013/0172581, US2013/0172582, US2013/0172583, US2013/0172584, US2013/0172585, US2013/0109869, US2012/0157697 and US2011/0213112, substantial demand is had for the further improvements in methods for producing furfural from biomass, this improves and the economy contributing to furans product is realized, and this furans product can be hydrogenated as THF.
The US2013/0172584 of the people such as Corbin is the representative of the method taked in these files, and wherein furfural is by comprising C
5sugar and/or C
6the aqueous materials solution solvent (as tetramethylene sulfone) miscible with the high boiling of heating and water of sugar and solid acid catalyst mix and produce.More particularly, describe a kind of reactive distillation process, wherein this aqueous materials solution is added into one and is included in the reactor of the solid acid catalyst in the high boiling organic solvent miscible with water and from the temperature of 100 degrees Celsius to 250 degrees Celsius and the pressure from 0MPa to 0.21MPa, is carrying out dehydration reaction in this embodiment.Remove the mixture of a kind of water and furfural at head space from the distillation column being arranged in this reactor head, via back up through multistage distillation to make to lose " minimizing " at the organic solvent miscible with water of head space, this high boiling organic solvent miscible with water is used to keep by product (as humin substances) dissolve and prevent them to be deposited on solid catalyst simultaneously.In the continuous print embodiment described in reference paper, the content at least partially of this reactor by a strainer or sieve pumping to prevent the suction of this solid acid catalyst, and then use or aqueous materials solution water or simply water dilution to precipitate water-insoluble by product from the solution in this high boiling solvent miscible with water.Then by filtering or these water-insoluble by products of centrifugal segregation.
But, to have sizable expense by this high boiling solvent miscible with water of Distillation recovery, simultaneously this solvent of recirculation will probably relate to by product accumulation within the system and perhaps by precipitating and filtering or the centrifugal accumulation not having the humin substances of the remnants of removal.When toluene preferably as this lower boiling, immiscible solvent is used for of the present invention with water substantially time, other benefit multiple can be realized equally.First, toluene is a kind of solvent than the high boiling solvent miscible with water (as tetramethylene sulfone) considerably cheaper.Toluene can expediently for one according in the method subsequently of WO ' 783 or easily can be separated with furfural, although although it is that obviously received and expensive in addition high boiling solvent will probably lose in the further step removing humin substances, this solid catalyst and salt from bottoms that some of the high boiling solvent miscible with water by contrast in the distillation of the furfural/water of head space are lost in the method for the people such as Corbin.In addition, the removal process of these bottoms of humin substances, this solid catalyst and salt and the regeneration of the supposition of this solid acid catalyst represent a large amount of additional processing cost, but, use a kind of lower boiling, allow these salt and acid catalyst recirculation directly for further use with the immiscible solvent of water.Finally, in the method for the people such as Corbin, remaining hexose can form additional humin substances, makes downstream processing and reclaim furfural more complicated.
Claims (40)
1., for manufacturing a method for ethanol and furfural from the mixture of pentose and hexose, the method comprises:
A) make the fermented mixture of a kind of hexose and pentose so that hexose is in the mixture converted into ethanol;
B) pentose is in the mixture any change into sugar alcohol substantially before terminate this fermentation;
C) by the separation of ethanol formed in the unconverted pentose in this mixture and this fermentation to produce a kind of alcohol product; And
D) the unconverted dehydration of pentoses making these be separated and be cyclized into furfural; And
E) a kind of furfural product is reclaimed.
2. method according to claim 1, is included in this separating step c further) before, the ethanol of the fermentation from the hexose of amylaceous fermented ethanol in the mixture from this pentose and hexose is combined.
3. method according to claim 2, wherein makes the hexose in the mixture of starch and this pentose and hexose be combined, and makes this starch ferment to provide this alcohol product together with hexose.
4. method according to claim 2, wherein this makes dehydration of pentoses and is cyclized into furfural to use a kind of water-soluble acid catalyst at high temperature at a kind of lower boiling, immiscible organic solvent completes under existing with water substantially.
5. method according to claim 1, wherein this makes dehydration of pentoses and is cyclized into furfural to use a kind of water-soluble acid catalyst at high temperature at a kind of lower boiling, immiscible organic solvent completes under existing with water substantially.
6. method according to claim 4, wherein this lower boiling, immiscible organic solvent is selected from toluene, ethanol, tetrahydrofuran (THF) and methyltetrahydrofuran with water substantially.
7. method according to claim 5, wherein this lower boiling, immiscible organic solvent is selected from toluene, ethanol, tetrahydrofuran (THF) and methyltetrahydrofuran with water substantially.
8. method according to claim 4, wherein this water-soluble acid catalyst is selected from sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid, formic acid, AlCl
36H
2o and mixture any in them.
9. method according to claim 5, wherein this water-soluble acid catalyst is selected from sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid, formic acid, AlCl
36H
2o and mixture any in them.
10. method according to claim 4, wherein by the furfural extraction that formed in the method to this lower boiling, with the immiscible solvent of water.
11. methods according to claim 5, wherein by the furfural extraction that formed in the method to this lower boiling, with the immiscible solvent of water.
12. methods according to claim 10, wherein this make dehydration of pentoses and be cyclized into furfural and by furfural extraction to this lower boiling, with the immiscible solvent of water in complete in series reaction device, wherein the upstream of each reactor add lower boiling, with the immiscible solvent of water and the furfural wherein partly reclaimed after each reactor in organic fraction.
13. methods according to claim 11, wherein this make dehydration of pentoses and be cyclized into furfural and by furfural extraction to this lower boiling, with the immiscible solvent of water in complete in series reaction device, wherein the upstream of each reactor add lower boiling, with the immiscible solvent of water and the furfural wherein partly reclaimed after each reactor in organic fraction.
14. methods according to claim 12, comprise further and collect these organic fraction, flash off from collected organic fraction lower boiling, with the immiscible solvent of water and then distill residuum to provide a kind of furfural product.
15. methods according to claim 13, comprise further and collect these organic fraction, flash off from collected organic fraction lower boiling, with the immiscible solvent of water and then distill residuum to provide a kind of furfural product.
16. methods according to claim 12, comprise further after each reactor collect comprise the aqueous portion of this water-soluble acid catalyst and the aqueous portion collected by recirculation for recycling in this dehydration and cyclisation step.
17. methods according to claim 13, comprise further after each reactor collect comprise the aqueous portion of this water-soluble acid catalyst and the aqueous portion collected by recirculation for recycling in this dehydration and cyclisation step.
18. methods according to claim 12, wherein this lower boiling, be toluene with the immiscible solvent of water and comprise further make to be extracted to furfural in this toluene catalytically decarbonylation to provide furans.
19. methods according to claim 13, wherein this lower boiling, be toluene with the immiscible solvent of water and comprise further make to be extracted to furfural in this toluene catalytically decarbonylation to provide furans.
20. method according to claim 18, comprise further and furans is catalytically hydrogenated to tetrahydrofuran (THF).
21. method according to claim 19, comprise further and furans is catalytically hydrogenated to tetrahydrofuran (THF).
22. methods according to claim 1, wherein the mixture of this pentose and hexose obtains from the fractionation of lignocellulose biomass, and this fractionation comprises the hydrolysis of Mierocrystalline cellulose in these biomass and hemicellulose.
23. methods according to claim 22, the Mierocrystalline cellulose wherein in these biomass and the hydrolysis of hemicellulose are completed by a kind of water soluble acid, and this water soluble acid is used to this dehydration of pentoses of catalysis subsequently and is cyclized into furfural.
24. methods according to claim 1, wherein the mixture of this pentose and hexose is the material by the at high temperature acid hydrolysis generation of whole biomass.
25. methods according to claim 25, the acid-hydrolyzed acid wherein for these whole biomass is a kind of water soluble acid, and this water soluble acid is used to this dehydration of pentoses of catalysis subsequently and is cyclized into furfural.
26. 1 kinds of methods for the mixture manufacture furfural from pentose and hexose, the method comprises:
A) make the fermented mixture of a kind of hexose and pentose so that hexose is in the mixture converted into ethanol;
B) pentose is in the mixture any change into sugar alcohol substantially before terminate this fermentation;
C) make the unconverted dehydration of pentoses in this fermented liquid and be cyclized into furfural; And
D) furfural so formed is isolated.
27. methods according to claim 26, wherein this make dehydration of pentoses and be cyclized into furfural be use a kind of water-soluble acid catalyst at high temperature being a kind ofly added in this fermented liquid, by furfural extraction to lower boiling wherein, immiscible organic solvent completes under existing with water substantially.
28. methods according to claim 27, wherein the formation of furfural and extraction are continuously and side by side carry out.
29. methods according to claim 28, wherein this make dehydration of pentoses and be cyclized into furfural and by furfural extraction to this lower boiling, with the immiscible solvent of water in complete continuously in order in series reaction device, wherein the upstream of each reactor add this lower boiling, with the immiscible solvent of water and the furfural wherein partly reclaimed after each reactor in organic fraction.
30. methods according to claim 29, comprise further and collect these organic fraction, flash off from collected organic fraction lower boiling, with the immiscible solvent of water and then distill residuum to provide a kind of furfural product.
31. methods according to claim 29, wherein this lower boiling, be toluene with the immiscible solvent of water and comprise further make to be extracted to furfural in this toluene catalytically decarbonylation to provide furans.
32. method according to claim 31, comprise further and furans is catalytically hydrogenated to tetrahydrofuran (THF).
33. methods according to claim 26, wherein the mixture of this pentose and hexose obtains from the fractionation of lignocellulose biomass, and this fractionation comprises the hydrolysis of Mierocrystalline cellulose in these biomass and hemicellulose.
34. methods according to claim 33, the Mierocrystalline cellulose wherein in these biomass and the hydrolysis of hemicellulose are completed by a kind of water soluble acid, and this water soluble acid is used to this dehydration of pentoses of catalysis subsequently and is cyclized into furfural.
35. methods according to claim 26, wherein the mixture of this pentose and hexose is the material by the at high temperature acid hydrolysis generation of whole biomass.
36. method according to claim 35, wherein these whole biomass comprise corn grain fiber.
37. methods according to claim 35, the acid-hydrolyzed acid wherein for these whole biomass is a kind of water soluble acid, and this water soluble acid is used to this dehydration of pentoses of catalysis subsequently and is cyclized into furfural.
38. 1 kinds for manufacturing the continuation method of furfural from the mixture of pentose and hexose, this continuation method comprises and a) uses a kind of water-soluble acid catalyst in series reaction device, make the dehydration of pentoses in this mixture in order and be cyclized into furfural, b) a kind of lower boiling is added in the upstream of each reactor, with the part of the immiscible solvent of water be used for after each reactor selectively by furfural extraction in organic fraction, c) collect these organic fraction and d) from collected organic fraction, flash off lower boiling, then e) residuum is distilled to provide a kind of furfural product with the immiscible solvent of water.
39. 1 kinds for manufacturing the continuation method of furans from the mixture of pentose and hexose, this continuation method comprises and a) uses a kind of water-soluble acid catalyst in series reaction device, make the dehydration of pentoses in this mixture in order and be cyclized into furfural, b) a kind of lower boiling is added in the upstream of each reactor, with the part of the immiscible solvent of water be used for after each reactor selectively by furfural extraction in organic fraction, c) these organic fraction are collected, d) by the furfural in collected organic fraction catalytically decarbonylation become furans, and e) comprise this lower boiling by distillation from one, furans product is separated with the residuum of the immiscible solvent of water.
40. according to method according to claim 38, comprise further and this furans product is hydrogenated to tetrahydrofuran (THF).
Applications Claiming Priority (3)
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| US201461942188P | 2014-02-20 | 2014-02-20 | |
| US61/942,188 | 2014-02-20 | ||
| PCT/US2015/013192 WO2015126581A1 (en) | 2014-02-20 | 2015-01-28 | Process for making furfural |
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| CN105378092A true CN105378092A (en) | 2016-03-02 |
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| EP (1) | EP2931906A4 (en) |
| JP (1) | JP2017506083A (en) |
| KR (1) | KR20160120196A (en) |
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| CN109219599A (en) * | 2016-06-03 | 2019-01-15 | 纳幕尔杜邦公司 | Use the method for organic solvent unmixing with water production furfural |
| CN109890802A (en) * | 2016-11-01 | 2019-06-14 | 国际壳牌研究有限公司 | The method for recycling furfural |
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| JP6961963B2 (en) | 2016-04-01 | 2021-11-05 | 三菱ケミカル株式会社 | Furfural manufacturing method |
| TWI768017B (en) * | 2017-05-30 | 2022-06-21 | 日商保土谷化學工業股份有限公司 | Process for producing bio-based polyether polyol, bio-based polyether polyol and bio-based polyurethane resin |
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|---|---|---|---|---|
| US2846449A (en) | 1956-08-15 | 1958-08-05 | Du Pont | Production of tetrahydrofuran |
| US5562777A (en) | 1993-03-26 | 1996-10-08 | Arkenol, Inc. | Method of producing sugars using strong acid hydrolysis of cellulosic and hemicellulosic materials |
| US7956203B2 (en) | 2000-03-27 | 2011-06-07 | E. I. Du Pont De Nemours And Company | Oxidation of 5-(hydroxymethyl) furfural to 2,5-diformylfuran and subsequent decarbonylation to unsubstituted furan |
| CA2653706C (en) * | 2006-06-06 | 2015-05-12 | Wisconsin Alumni Research Foundation | Catalytic process for producing furan derivatives from carbohydrates in a biphasic reactor |
| EP2513080B1 (en) * | 2009-12-16 | 2015-07-29 | Shell Internationale Research Maatschappij B.V. | Method for producing furfural from lignocellulosic biomass material |
| US8524924B2 (en) | 2010-12-21 | 2013-09-03 | E I Du Pont De Nemours And Company | Process for furfural production from biomass |
| US9024047B2 (en) * | 2010-12-21 | 2015-05-05 | E I Du Pont De Nemours And Company | Methods for furfural production from branched non-fermentable sugars in stillage or syrup |
| US10108783B2 (en) | 2011-07-05 | 2018-10-23 | Saudi Arabian Oil Company | Systems, computer medium and computer-implemented methods for monitoring health of employees using mobile devices |
| CN103958689A (en) | 2011-09-23 | 2014-07-30 | 阿彻丹尼尔斯米德兰德公司 | C1-C2 organic acid treatment of lignocellulosic biomass to produce acylated cellulose pulp, hemicellulose, lignin and sugars and fermentation of the sugars |
| US8524925B2 (en) | 2011-10-31 | 2013-09-03 | E I Du Pont De Nemours And Company | Production of furfural from biomass |
| CA2859898A1 (en) | 2011-12-28 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Process for the production of furfural |
| WO2013102007A1 (en) | 2011-12-28 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Process for the production of furfural |
| WO2013102000A1 (en) | 2011-12-28 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Process for the production of furfural |
| US9181210B2 (en) | 2011-12-28 | 2015-11-10 | E I Du Pont De Nemours And Company | Processes for making furfurals |
| WO2013102027A1 (en) | 2011-12-28 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Process for the production of furfural |
| BR112014015988A8 (en) | 2011-12-28 | 2017-07-04 | Du Pont | process |
| EP2872495B1 (en) * | 2012-07-13 | 2016-08-24 | DSM IP Assets B.V. | Process for the production of furfural and levulinic acid from lignocellulosic biomass |
| US9538658B2 (en) | 2012-07-18 | 2017-01-03 | Zte (Usa) Inc. | Compact low loss transition with an integrated coupler |
-
2015
- 2015-01-28 KR KR1020157025880A patent/KR20160120196A/en not_active Application Discontinuation
- 2015-01-28 JP JP2016570768A patent/JP2017506083A/en active Pending
- 2015-01-28 EP EP15725223.0A patent/EP2931906A4/en not_active Withdrawn
- 2015-01-28 CA CA2897613A patent/CA2897613A1/en not_active Abandoned
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- 2015-01-28 CN CN201580001288.7A patent/CN105378092A/en active Pending
- 2015-05-22 BR BR112015016768A patent/BR112015016768A2/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109219599A (en) * | 2016-06-03 | 2019-01-15 | 纳幕尔杜邦公司 | Use the method for organic solvent unmixing with water production furfural |
| CN109219599B (en) * | 2016-06-03 | 2023-10-31 | 纳幕尔杜邦公司 | Method for producing furfural using a water-immiscible organic solvent |
| CN109890802A (en) * | 2016-11-01 | 2019-06-14 | 国际壳牌研究有限公司 | The method for recycling furfural |
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| Publication number | Publication date |
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| EP2931906A4 (en) | 2016-07-13 |
| KR20160120196A (en) | 2016-10-17 |
| JP2017506083A (en) | 2017-03-02 |
| BR112015016768A2 (en) | 2017-07-11 |
| CA2897613A1 (en) | 2015-08-20 |
| WO2015126581A1 (en) | 2015-08-27 |
| EP2931906A1 (en) | 2015-10-21 |
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