CN102321055A - Method for preparing 5-hydroxymethylfurfural from woody biomasses - Google Patents
Method for preparing 5-hydroxymethylfurfural from woody biomasses Download PDFInfo
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Abstract
The invention relates to a method for preparing 5-hydroxymethylfurfural (HMF) from cellulose-rich woody biomasses. The method comprises the following steps of: 1) pretreating the cellulose-rich biomasses by using ionic liquid, and separating to remove hemicelluloses and lignin to obtain cellulose; 2) dissolving the cellulose obtained in the step 1) into the ionic liquid, adding a catalyst, heating to 100 to 160 DEG C, and reacting with mechanical stirring for 10 minutes to 8 hours; 3) after the reaction is finished, diluting the reaction solution by adding diluent and extracting the 5-HMF by adding an extracting agent to obtain an organic phase; and 4) distilling under reduced pressure to remove the organic phase to obtain the product 5-hydroxymethylfurfural. The method is simple and practicable. By the method, influence of lignin on the reaction in the process of transforming vegetable fiber into the 5-hydroxymethylfurfural is effectively reduced; the separation and purification process of the 5-hydroxymethylfurfural is simplified; and the preparation efficiency of the 5-hydroxymethylfurfural is improved.
Description
Technical field
The present invention relates to the method that a kind of Wooden Biomass is converted into chemical; Being particularly related to a kind of is the method for feedstock production 5 hydroxymethyl furfural with the Wooden Biomass; Particularly, the present invention relates to a kind of is that medium is the method for 5 hydroxymethyl furfural with the cellulose conversion in the Wooden Biomass with the ionic liquid.
Background technology
At present, fossil oil mainly is oil, coal and Sweet natural gas etc., is still topmost fuel source in the world wide.But because the non-renewable characteristics of fossil resource; Coal, oil, Sweet natural gas etc. belong to disposable Nonrenewable energy resources, according to measuring and calculating, present fossil energy; Will be totally at following 100 years internal consumptions, obviously fossil energy can not satisfy human growing energy demand.
Under this background, consider the sustainability, wide material sources property, security of the energy etc., the research of producing the energy and chemical with the renewable biomass resource has become the hot issue in energy research field.The potential amount of occurring in nature Wooden Biomass is very huge; The annual vegetable fibre amount that is produced by photosynthesis can reach 1,800 hundred million tons; Be equivalent to 10 times of the annual total energy consumption in the whole world; It can satisfy the present mankind's energy demand fully, so the utilization of Wooden Biomass, has become one of development trend of future source of energy.
The staple of vegetable fibre is Mierocrystalline cellulose (40%～50%), semicellulose (15%～25%) and xylogen (15～30%).Mierocrystalline cellulose, half fiber, xylogen is cross-linked with each other through hydrogen bond, forms stable structure, makes its conversion difficulty very that becomes.
The most frequently used vegetable fibre method for transformation is hydrolysis, comprises mineral acid hydrolysis and enzymic hydrolysis.It is converted into vegetable fibre small molecules such as monose, and then these monose small molecules are converted into valuable hardware and software platform compounds such as hydroxymethylfurfural, furfural, levulinic acid.In said hardware and software platform compound, 5 hydroxymethyl furfural is a kind of important hardware and software platform compound, and it can be used for substituting the production that numerous monomer in the present polymer industry is realized polymkeric substance; In addition; 5 hydroxymethyl furfural also can be used for producing 2, the 4-dimethyl furan, and the additive that acts as a fuel uses.Therefore directly be that raw material is produced 5 hydroxymethyl furfural with the vegetable fibre, be the research and development emphasis always.
Mineral acid hydrolysis, it utilizes acid or alkali to carry out pre-treatment earlier, removes semicellulose and xylogen, utilizes mineral acid as catalyzer again, under HTHP, reacts.Typical mineral acid hydrolysis technology is shown in WO2007/051269A1; Ligno-cellulosic materials is in the different water flat bed charging of reactor drum (10), and contacts with xylogen organic solvent, water and extremely rare strong inorganic acid solution, with the hydrolysis extract that obtains liquid phase and the unreacted and the undissolved material of solid phase; Different horizontal layer with controlled vapor stream injecting reactor (10); So that enough temperature of organic solvent and strong inorganic acid to be provided, and generate desirable product (sugar), liquid phase stream recycling on reactor drum (10) different horizontal layer; Its remainder takes out from reactor drum (10); Cool off to obtain enriched material through solvent evaporation, shift xylogen through decant, and enriched material is transferred to subsequent process steps suddenly.
The vice proper of mineral acid hydrolysis technology is, hydroxymethylfurfural less stable in the aqueous solution, and very easily the hydration degraded generates levulinic acid, and the efficient that causes this method to be produced thus is not high.In addition, owing to use acid under HTHP, to react, the erosion resistance and the resistance to pressure of reaction vessel all had higher requirements as catalyzer.
Another method of utilizing vegetable fibre is enzymic hydrolysis.Typical lignocellulose enzyme hydrolysis process is shown in WO2009/046524, and said enzyme hydrolysis process comprises: a) use first zymin that raw material is carried out first enzymic hydrolysis process, obtain odor component stream and low viscous flow and effluent; B) use second zymin that low viscous flow is effluented and carry out second enzymic hydrolysis process, obtain rich sacchariferous process flow.Said first zymin has about 50% to about 90% active and about 50% to 10% the cellulase activity of semicellulose; Said second zymin comprises beta-glucosidase and cellulase; Wherein beta-glucosidase and cellulase act preferentially on cellobiose and cellulosic β-1,4 key.
Though enzyme hydrolysis method has the advantage that the mineral acid hydrolysis method is not had because the speed of reaction of enzymolysis is slow, and receives easily from the influence of various biomass components enzyme lost activity, this big limitations the industrial application of enzyme hydrolysis method.
In recent years, a kind of method of new conversion plant fiber material is developed.Utilize ionic liquid as solvent, can under relatively mild condition, realize the conversion of vegetable fibre.
Binder etc. " Simple chemical transformation of lignocellulosic biomass into furans for fuels and chemicals; Binder; J.B et al, Jounal of the America Chemical Society, 2009; 131 (5): 1979-1985 " utilize the DMAc-LiCl system, with CrCl
3With HCl be catalyzer, realized the conversion of corn straw, the hydroxymethylfurfural of acquisition and the yield of furfural are respectively 48% and 34%.
Zhang etc. " Direct conversion of glucose and cellulose to 5-hydroxymethylfurfural in ionic liquid under microwave irradiation; Tetrahedron Letters; 2009; 50 (38): 5403-5405 " utilize ionic liquid as medium under the condition of microwave heating, CrCl
3As catalyzer, realized corn straw, the conversion of straw and pine.The yield of 5 hydroxymethyl furfural and the yield of furfural are respectively 45%-52% and 23%-31%.
CN 101289817A disclose a kind of in ionic liquid the cellulosic method of effectively hydrolyzing; Ionic liquid with dissolved cellulose is a solvent, is reactant with the water of >=1 molar equivalent, is catalyzer with catalytic amount to stoichiometric mineral acid; Mierocrystalline cellulose reacted 2 minutes～9 hours in 70 ℃～100 ℃ under normal pressure; After reaction finishes,, promptly get cellulosic hydrolysate with cold water cancellation reaction, with the alkali neutralization.Total reducing sugars in the hydrolyzed solution and glucose are carried out quantitative chemical analysis, and the result shows that reducing sugar yield reaches as high as 73%, and corresponding glucose productive rate reaches 53%.
CN 101333777A disclose a kind of in ionic liquid the method for effectively hydrolyzing lignocellulose raw material; With the ionic liquid is solvent, is reactant with the water of >=1 molar equivalent, is catalyzer with catalytic amount to stoichiometric mineral acid or organic acid; Lignocellulose raw material such as agricultural crop straw, pine powder under normal pressure in not being higher than under 100 ℃ the temperature reaction 2 minutes～34 hours; After reaction finishes,, promptly get hydrolyzed solution with cold water cancellation reaction, with the alkali neutralization; Total reducing sugars in the hydrolyzed solution is carried out quantitative chemical analysis, and the result shows that reducing sugar yield reaches as high as 81%, and hydrolysis efficiency reaches 58%.
Though above-mentioned research has successfully realized with the vegetable fibre being that raw material directly prepares 5 hydroxymethyl furfural; But each component owing to vegetable fibre in reaction process; Comprise all participation reactions in system of Mierocrystalline cellulose, semicellulose and xylogen; So cause reacting the product component complicacy of generation, for the later separation of reaction is brought difficulty.Simultaneously, the multiple material that system exists also may impact the yield of 5 hydroxymethyl furfural, and this has also limited its industrial application.
Summary of the invention
To the deficiency of prior art, it is medium with the ionic liquid that one of the object of the invention is to provide a kind of, realizes with the cellulose conversion in the Wooden Biomass being the method for 5 hydroxymethyl furfural.
In the vegetable fibre of common rich cellulose, there are semicellulose and xylogen simultaneously.For improving the efficient that 5 hydroxymethyl furfural transforms, reduce the separation costs of 5 hydroxymethyl furfural, be necessary three components of separating plant fiber in advance, transform separately again.
Of the present invention a kind of be medium with the ionic liquid, realize lignocellulose is converted into the method for 5 hydroxymethyl furfural, concrete steps are following:
1) vegetable fibre after the drying and crushing is carried out pre-treatment with ionic liquid, remove semicellulose and xylogen, the Mierocrystalline cellulose that obtains is used the water washing after drying.
2) the resulting Mierocrystalline cellulose of step 1) is added in the ionic liquid according to 4wt%～20wt%, add catalyzer again, be warmed up to 60～160 ℃ of temperature of reaction, reaction 10min～8h.
3) to step 2) add thinner and extraction agent in the resulting reaction mixture, through the mode of extraction the 5 hydroxymethyl furfural in the mixed solution is come together to organic phase.
4) utilize the mode of underpressure distillation to steam the resulting extraction phase that contains 5 hydroxymethyl furfural of step 3), obtain the 5 hydroxymethyl furfural product except that organic solvent.
As preferably, said method comprising the steps of:
1) ionic liquid is mixed with Wooden Biomass; Heating 4-48h under common oil bath or microwave condition under 80～140 ℃; Filtering separation obtains filtrating, in filtrating, adds entry/DMSO (DMSO 99.8MIN.) mixed solvent washing extraction repeatedly, and it is Mierocrystalline cellulose that filtering separation obtains solid matter;
2) the resulting Mierocrystalline cellulose of step 1) is added in the ionic liquid according to 4wt%～20wt%, add catalyzer again, be heated to 60～160 ℃ of temperature of reaction, reaction 10min～8h obtains reaction mixture;
3) to step 2) add thinner and extraction agent in the resulting reaction mixture, behind the thorough mixing, leave standstill, extracting and separating obtains containing the extraction phase of 5 hydroxymethyl furfural;
4) the resulting extraction phase that contains 5 hydroxymethyl furfural of step 3) is removed organic solvent through underpressure distillation, obtain the 5 hydroxymethyl furfural product.
According to of the present invention be that medium is the method for 5-HMF with the cellulose conversion in the Wooden Biomass with the ionic liquid, the Wooden Biomass raw material comprises one or more in wood chip, stalk, crop seeds cot and the residue in the said step 1).
According to of the present invention be that medium is the method for 5-HMF with the cellulose conversion in the Wooden Biomass with the ionic liquid; The ionic liquid reaction solution concentration (mass concentration) preferred 3～8% that contains plant fiber material in the said step 1); Further preferred 3～6%, more preferably 4～6%.
According to of the present invention be that medium is the method for 5-HMF with the cellulose conversion in the Wooden Biomass with the ionic liquid, said step 2) in cellulosic mass concentration be 4wt%-20wt%, preferred 5wt-15wt%, more preferably 6wt%-10wt%.
According to of the present invention be that medium is the method for 5-HMF with the cellulose conversion in the Wooden Biomass with the ionic liquid, said step 2) in used catalyzer for containing the compound of chromium (II) and chromium (III), the for example halogenide of chromium and hydrate thereof, nitrate salt etc.The preferred muriate of said halogenide.
According to of the present invention be that medium is the method for 5-HMF with the cellulose conversion in the Wooden Biomass with the ionic liquid; Said step 2) used catalyst ratio is 1mol%-25mol% (is benchmark with the Mierocrystalline cellulose anhydroglucose) in; Preferred 4mol%-20mol% is preferably 6mol%-15mol%.
According to of the present invention be that medium is the method for 5-HMF with the cellulose conversion in the Wooden Biomass with the ionic liquid; Said step 2) temperature of reaction in is 60～160 ℃; Be preferably 70～150 ℃, more preferably 90～130 ℃, the reaction times is 10min～8h; Preferred 30min～6h, more preferably 2h-6h.
According to of the present invention be that medium is the method for 5-HMF with the cellulose conversion in the Wooden Biomass with the ionic liquid; Described can dissolving cellulos and xylogen and realize that the ionic liquid of cellulose conversion is the imidazoles halogen; Preferably, described imidazoles halogen is the imidazoles villaumite.
According to of the present invention be that medium is the method for 5-HMF with the cellulose conversion in the Wooden Biomass with the ionic liquid, the positively charged ion of wherein said imidazoles halogen has following formula (I) structure:
In this structural formula, R
1And R
2Be C
1-C
20Alkyl, thiazolinyl or aryl, R
3, R
4, R
5Be independently selected from hydrogen, C
1-C
20Alkyl, alkoxyl group, thiazolinyl and aryl;
Preferably, the positively charged ion of described imidazoles halogen has formula (II) structure:
In this structural formula, R
1And R
2Be C
1-C
20Alkyl, thiazolinyl or aryl;
More preferably, the positively charged ion of described imidazoles halogen has formula (III) structure:
In this structural formula, R
1Be C
1-C
20Alkyl, thiazolinyl or aryl.
According to of the present invention be that medium is the method for 5-HMF with the cellulose conversion in the Wooden Biomass with the ionic liquid, used thinner is lower boiling solvent in the said step 3), for example water, methyl alcohol, ethanol etc. or its mixture.
According to of the present invention be that medium is the method for 5-HMF with the cellulose conversion in the Wooden Biomass with the ionic liquid, thinner additional proportion used in the said step 3) is 0.5: 1～5: 1, is preferably 1: 1～2: 1.
According to of the present invention be that medium is the method for 5-HMF with the cellulose conversion in the Wooden Biomass with the ionic liquid, used extraction agent is the lower boiling non-polar solvent in the said step 3), preferable methyl isobutyl ketone, ETHYLE ACETATE, ether etc. or its mixture.
According to of the present invention be that medium is the method for 5-HMF with the cellulose conversion in the Wooden Biomass with the ionic liquid, extraction agent additional proportion used in the said step 3) is 5: 1～30: 1, is preferably 8: 1～25: 1, more preferably 10: 1～20: 1.
The present invention has following advantage:
1, compare with the method that traditional concentrated acid dehydration prepares 5-HMF, the present invention has avoided the use of mineral acid, so reactor drum need not to use corrosion resistant material;
2, with the reacting phase ratio of traditional water solution, the yield of 5-HMF of the present invention significantly improves, and reaction conditions is gentle, and technology is simple, and cost is low;
3, be that 200980115239.0 patent is compared with application number, the present invention directly utilizes vegetable fibre as raw material, greatly reduces the technology cost in the raw material;
4, be that 200980122910.4 patent is compared with application number, the present invention utilizes ionic liquid as the medium that transforms vegetable fibre, has avoided use N, high boiling organic solvent such as dinethylformamide;
5, present method utilizes ionic liquid earlier the Mierocrystalline cellulose in the vegetable fibre to be separated; And then transform; Reduce the complexity of reacting in the reaction process effectively, reduced the content of other reaction product in the reaction mixture, helped the separation of product 5-HMF.
Description of drawings
Fig. 1 handles plant fiber material and realizes the schematic flow sheet that Mierocrystalline cellulose transforms to 5 hydroxymethyl furfural with ionic liquid for of the present invention
Fig. 2 is the liquid phase spectrogram of cellulose degradation product
Embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment only is used for helping to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment 1
Take by weighing the about 10.0g of pine sawdust, mixing solutions (mass ratio 6: the 1) 50.0g of ionic liquid 1-allyl group-3-Methylimidazole villaumite (AmimCl) and DMSO puts into round-bottomed flask, microwave heating to 100 ℃, and intense mechanical stirred 4 hours.Reaction finishes, and uses 300 order stainless steel filtering net filtering separation, in filtrating, adds elutriation and goes out Mierocrystalline cellulose and xylogen.(1: 1v) washing is 8 times, obtains pine Mierocrystalline cellulose and the washings that contains xylogen with 200 order nylon filter cloth filtering separation with the DMSO/ aqueous solution with this mixture.The pine Mierocrystalline cellulose is put into vacuum drying oven, and 60 ℃ of oven dry 24h obtain cellulose prods 3.0g.The Mierocrystalline cellulose of gained is added in the 30ml ionic liquid, and add CrCl
36H
2O0.2g is heated to 120 ℃ under stirring, and reacts 6 hours.After reaction finished, to wherein adding 100ml water, diluted reaction mixture utilized 500ml extraction agent mibk to divide the product in the extraction solution five times.The extraction phase that contains 5-HMF of underpressure distillation gained, the yield of 5 hydroxymethyl furfural can reach 50%.
Embodiment 2
With the pine sawdust is raw material, and 1-allyl group-3-Methylimidazole villaumite is a reaction medium, and cellulosic preparation is with embodiment 1.The Mierocrystalline cellulose that takes by weighing the 3.0g gained adds in the 30ml ionic liquid, and adds CrCl
36H
2O0.2g is heated to 100 ℃ under stirring, and reacts 8 hours.After reaction finished, to wherein adding 30ml water, diluted reaction mixture utilized 800ml extraction agent mibk to divide the product in the extraction solution five times.The extraction phase that contains 5-HMF of underpressure distillation gained, the yield of 5 hydroxymethyl furfural can reach 45%.
Embodiment 3
With the pine sawdust is raw material, and 1-allyl group-3-Methylimidazole villaumite is a reaction medium, and cellulosic preparation is with embodiment 1.The Mierocrystalline cellulose that takes by weighing the 3.0g gained adds in the 40ml ionic liquid, and adds CrCl
36H
2O0.2g is heated to 140 ℃ under stirring, and reacts 1 hour.After reaction finished, to wherein adding 60ml water, diluted reaction mixture utilized 300ml extraction agent mibk to divide the product in the extraction solution five times.The extraction phase that contains 5-HMF of underpressure distillation gained, the yield of 5 hydroxymethyl furfural can reach 55%.
Embodiment 4
With the pine sawdust is raw material, and 1-allyl group-3-Methylimidazole villaumite is a reaction medium, and cellulosic preparation is with embodiment 1.The Mierocrystalline cellulose that takes by weighing the 3.0g gained adds in the 30ml ionic liquid, and adds CrCl
36H
2O0.18g is heated to 90 ℃ under stirring, and reacts 12 hours.After reaction finished, to wherein adding 40ml water, diluted reaction mixture utilized 500ml extraction agent ETHYLE ACETATE to divide the product in the extraction solution five times.The extraction phase that contains 5-HMF of underpressure distillation gained, the yield of 5 hydroxymethyl furfural can reach 47%.
Embodiment 5
With the pine sawdust is raw material, and 1-allyl group-3-Methylimidazole villaumite is a reaction medium, and cellulosic preparation is with embodiment 1.The Mierocrystalline cellulose that takes by weighing the 2.5g gained adds in the 30ml ionic liquid, and adds CrCl
36H
2O0.2g is heated to 100 ℃ under stirring, and reacts 8 hours.After reaction finished, to wherein adding 40ml ethanol, diluted reaction mixture utilized 500ml extraction agent mibk to divide the product in the extraction solution five times.The extraction phase that contains 5-HMF of underpressure distillation gained, the yield of 5 hydroxymethyl furfural can reach 52%.
Embodiment 6
With bagasse is raw material, and 1-allyl group-3-Methylimidazole villaumite (AmimCl) is a medium, and cellulosic preparation takes by weighing the 2.0g Mierocrystalline cellulose and is dissolved in the 25ml ionic liquid with embodiment 1, adds CrCl
36H
2O 0.35g is heated to 140 ℃ under stirring, and reacts 40 minutes.After reaction finished, to wherein adding 45ml water, diluted reaction mixture utilized 500ml extraction agent mibk to divide the product in the extraction solution five times.The extraction phase that contains 5-HMF of underpressure distillation gained, the yield of 5 hydroxymethyl furfural can reach 42%.
Embodiment 7
With the pine sawdust is raw material, is reaction medium (BmimCl) with ionic liquid 1-butyl-3-Methylimidazole villaumite.Cellulosic preparation is with embodiment 1.The Mierocrystalline cellulose that takes by weighing the 3.0g gained is dissolved in the 30ml ionic liquid, adds CrCl
36H
2O 0.25g is warming up to 140 ℃ under stirring, and reacts 40 minutes.After reaction finished, to wherein adding 100ml water, diluted reaction mixture utilized 500ml extraction agent ETHYLE ACETATE to divide the product in the extraction solution five times.The extraction phase that contains 5-HMF of underpressure distillation gained, the yield of 5 hydroxymethyl furfural can reach 45%.
With the pine sawdust is raw material, is reaction medium (BmimCl) with ionic liquid 1-methyl-3-Methylimidazole villaumite.Cellulosic preparation is with embodiment 1.The Mierocrystalline cellulose that takes by weighing the 2.8g gained is dissolved in the 30ml ionic liquid, adds CrCl
36H
2O 0.22g is warming up to 130 ℃ under stirring, and reacts 60 minutes.After reaction finished, to wherein adding 50ml water, diluted reaction mixture utilized 500ml extraction agent ETHYLE ACETATE to divide the product in the extraction solution five times.The extraction phase that contains 5-HMF of underpressure distillation gained, the yield of 5 hydroxymethyl furfural can reach 45%.
Applicant's statement; The present invention explains detailed process condition of the present invention and technical process through the foregoing description; But the present invention is not limited to above-mentioned detailed process condition and technical process, does not mean that promptly the present invention must rely on above-mentioned detailed process condition and technical process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (8)
1. one kind is the method for feedstock production 5 hydroxymethyl furfural with the vegetable fibre, it is characterized in that said method comprises that step is following:
1) vegetable fibre after the drying and crushing is carried out pre-treatment with ionic liquid, remove semicellulose and xylogen, the Mierocrystalline cellulose that obtains is used the water washing after drying.
2) the resulting Mierocrystalline cellulose of step 1) is added in the ionic liquid according to 4wt%～20wt%, add catalyzer again, be warmed up to 60～160 ℃ of temperature of reaction, reaction 10min～8h.
3) to step 2) add thinner and extraction agent in the resulting reaction mixture, through the mode of extraction the 5 hydroxymethyl furfural in the mixed solution is come together to organic phase.
4) utilize the mode of underpressure distillation to steam the resulting extraction phase that contains 5 hydroxymethyl furfural of step 3), obtain the 5 hydroxymethyl furfural product except that organic solvent.
2. the method for claim 1 is characterized in that, said method comprising the steps of:
1) ionic liquid is mixed with Wooden Biomass, heating 4-48h under common oil bath or microwave condition under 80～140 ℃, filtering separation obtains filtrating, in filtrating, adds entry/DMSO mixed solvent washing and extracts repeatedly, and it is Mierocrystalline cellulose that filtering separation obtains solid matter;
2) the resulting Mierocrystalline cellulose of step 1) is added in the ionic liquid according to 4wt%～20wt%, add catalyzer again, be heated to 60～160 ℃ of temperature of reaction, reaction 10min～8h obtains reaction mixture;
3) to step 2) add thinner and extraction agent in the resulting reaction mixture, behind the thorough mixing, leave standstill, extracting and separating obtains containing the extraction phase of 5 hydroxymethyl furfural;
4) the resulting extraction phase that contains 5 hydroxymethyl furfural of step 3) is removed organic solvent through underpressure distillation, obtain the 5 hydroxymethyl furfural product.
3. according to claim 1 or claim 2 method is characterized in that the Wooden Biomass raw material comprises one or more in wood chip, stalk, crop seeds cot and the residue in the said step 1);
Preferably, it is preferred 3～8% to contain the ionic liquid reaction solution concentration (mass concentration) of plant fiber material in the said step 1), further preferred 3～6%, and more preferably 4～6%.
4. like the described method of one of claim 1-3, it is characterized in that said step 2) in cellulosic mass concentration be preferably 5-15%, more preferably 6wt%-10wt%;
Preferably, said step 2) catalyzer used in is for containing the compound of chromium (II) and chromium (III), the for example halogenide of chromium and hydrate thereof, nitrate salt etc.; The preferred muriate of said halogenide;
Preferably, said step 2) used catalyzer is a benchmark with the Mierocrystalline cellulose anhydroglucose in, and its ratio is 1mol%-25mol%, and preferred 4mol%-20mol% is preferably 6mol%-15mol%;
Preferably, said step 2) temperature of reaction in is preferably 70～150 ℃, and more preferably 90～130 ℃, preferred 30min～6h of reaction times, more preferably 2h-6h.
5. like the described method of one of claim 1-4, it is characterized in that said ionic liquid is the imidazoles halogen, preferably, described imidazoles halogen is the imidazoles villaumite.
6. method as claimed in claim 5 is characterized in that, the positively charged ion of described imidazoles halogen has following formula (I) structure:
Wherein, R
1And R
2Be C
1-C
20Alkyl, thiazolinyl or aryl, R
3, R
4, R
5Be independently selected from hydrogen, C
1-C
20Alkyl, alkoxyl group, thiazolinyl and aryl;
Preferably, the positively charged ion of described imidazoles halogen has formula (II) structure:
Wherein, R
1And R
2Be C
1-C
20Alkyl, thiazolinyl or aryl;
More preferably, the positively charged ion of described imidazoles halogen has formula (III) structure:
Wherein, R
1Be C
1-C
20Alkyl, thiazolinyl or aryl.
7. like the described method of one of claim 1-6, it is characterized in that used thinner is lower boiling solvent in the said step 3), preferably water, methyl alcohol, ethanol or its mixture.
8. like the described method of one of claim 1-7, it is characterized in that thinner additional proportion used in the said step 3) is 0.5: 1～5: 1, is preferably 1: 1～2: 1;
Used extraction agent is the lower boiling non-polar solvent in the said step 3), preferable methyl isobutyl ketone, ETHYLE ACETATE, ether etc. or its mixture;
Extraction agent additional proportion used in the said step 3) is 5: 1～30: 1, is preferably 8: 1～25: 1, more preferably 10: 1～20: 1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102617523A (en) * | 2012-03-09 | 2012-08-01 | 中南大学 | Method for preparing 5-hydroxymethylfurfural by hydrothermally decomposing wood fibers |
| CN103757959A (en) * | 2014-01-08 | 2014-04-30 | 中国科学院过程工程研究所 | New method for obtaining cellulose-rich material from straws by two-step method by adopting ionic liquids |
| CN104628684A (en) * | 2013-11-11 | 2015-05-20 | 中国科学院大连化学物理研究所 | Method for extracting 5-hydroxymethylfurfural from ionic liquid |
| CN104829560A (en) * | 2014-02-11 | 2015-08-12 | 中国科学院大连化学物理研究所 | Method of synthesizing 5-hydroxymethyl furfural |
| CN104923315A (en) * | 2015-05-29 | 2015-09-23 | 盐城工学院 | Solid acid catalyst TiP/ATP and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102617523A (en) * | 2012-03-09 | 2012-08-01 | 中南大学 | Method for preparing 5-hydroxymethylfurfural by hydrothermally decomposing wood fibers |
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| CN104628684B (en) * | 2013-11-11 | 2017-09-08 | 中国科学院大连化学物理研究所 | A kind of method that 5 hydroxymethylfurfurals are extracted from ionic liquid |
| CN103757959A (en) * | 2014-01-08 | 2014-04-30 | 中国科学院过程工程研究所 | New method for obtaining cellulose-rich material from straws by two-step method by adopting ionic liquids |
| CN104829560A (en) * | 2014-02-11 | 2015-08-12 | 中国科学院大连化学物理研究所 | Method of synthesizing 5-hydroxymethyl furfural |
| CN104923315A (en) * | 2015-05-29 | 2015-09-23 | 盐城工学院 | Solid acid catalyst TiP/ATP and preparation method and application thereof |
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