CN101812039B - Method for generating 5-hydroxymethylfurfural by using ionic liquid catalysis - Google Patents
Method for generating 5-hydroxymethylfurfural by using ionic liquid catalysis Download PDFInfo
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Abstract
The invention discloses a method for generating 5-hydroxymethylfurfural by using ionic liquid catalysis, which comprises the following steps: dissolving a reaction substrate into an organic solvent, and adding ionic liquid in an amount of 5 to 20 percent based on the total mole of the reaction substrate; and reacting the mixture for at least 2 hours at the temperature of between 70 and 120 DEG C under the protection of inert gas, namely neutralizing the reaction solution, and filtering, drying and distilling the reaction product to obtain the 5-hydroxymethylfurfural. The reaction system shows the characteristic of homogeneous reaction during catalytic dehydration, and has high catalytic activity and selectivity; and the using amount of a catalyst can be optimized to trace so as to improve the reaction conversion rate, reduce the use of other organic solvent and additive, reduce the cost and facilitate the separation and purification of the reaction product at the same time.
Description
Technical field
The present invention relates to a kind of method of synthetic 5 hydroxymethyl furfural, more particularly, relate to a kind of method of utilizing ionic liquid-catalyzed generation 5 hydroxymethyl furfural.
Background technology
Along with serious day by day energy dilemma and environmental pollution, People more and more is paid attention to the development and utilization of renewable resources biomass.At present, utilize fructose or glucose to become one of research focus through the synthetic 5 hydroxymethyl furfural (HMF) that dewaters for raw material.HMF is the important intermediate of compound probability organic chemicals; Platform as one " omnipotent "; It can react synthesizing new macromolecular material and many high value added products through hydrogenation, oxydehydrogenation, esterification, halogenation, polymerization, hydrolysis and other; Be widely used as medicine, resene plastics and fuel dope etc., make it be expected to become the breakthrough point that utilizes biomass resource to substitute petrochemical materials synthesis of chemicals route.
Generate in the process of HMF in the hexose dehydration, catalyzer commonly used comprises solid acid, mineral acid and metal chloride.Wherein, a) solid acid catalyst generally is a metal phosphate, and as with vanadium phosphorus oxide during as catalyzer, to generate the reaction yield of HMF be (Appl.Catal.A 275 (2004) 111) between the 32.9-59.6% to the dehydration of D-fructose under the different condition; B) with mineral acids such as HCl, H2SO4 or H3PO4 during as catalyzer; Generally to add methyl-sulphoxide (DMSO) and polypyrrole alkane ketone (PVP) is made additive; And need in water, mibk/2-butanols two-phase system, to react, the reaction yield of D-fructose catalysis being transformed into HMF is about 72% (Science 312 (2006) 1933 and Green Chem.9 (2007) 342) under this condition; C) make catalyzer with metal chromium ions (like CrCl2), when solvent was an ionic liquid 1-ethyl-3-Methylimidazole muriate, the reaction yield that D-fructose or gluconate dehydratase generate HMF was about 70% (Science 316 (2007) 1597).U.S. Pat 4740605 has been reported the method with the synthetic 5-hydroxymethylfurans aldehyde of the aqueous solution of inorganic acid as catalyst high-temperature catalytic sugar compounds; Patent US7317116B2 has reported process and the purification process thereof that uses the synthetic 5 hydroxymethyl furfural of Amberlyst35 catalysis fructose soln; In the above-mentioned catalystsystem, be the catalytic dehydration process that can only be applicable to D-fructose, and need to add a large amount of organic solvents and additive with the shortcoming of solid acid or inorganic acid as catalyst; When making catalyzer with chromium dichloride, shortcoming is that the toxicity of catalyzer is bigger.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, improve reaction conversion ratio, reduce the use of other organic solvents and additive, when reducing cost, help the separation and the purifying of reaction product.
The present invention provides a kind of and uses simple acidic ion liquid to promote the fructose dehydration reaction to produce the compound method of 5-hydroxymethylfurans aldehyde as catalyzer, and such reaction system shows the characteristics of even phase reaction in the catalytic dehydration process, and catalytic activity is high, and selectivity is higher; And catalyst levels can be optimized to trace, helps the separation and the purifying of reaction product.Reaction system is simple, environmental friendliness, and aftertreatment is easy, and production cost is low, the no hidden danger of safety.
A kind of method of utilizing ionic liquid-catalyzed generation 5 hydroxymethyl furfural of the present invention, carry out according to following step:
(1) reaction substrate is dissolved in the solvent, adds ionic liquid again, said ion liquid add-on is the 5-20% of reaction substrate mole number;
(2) reacted at least 2 hours down at 70-120 ℃, can pass through neutralization reaction solution, filter, drying, distillation obtains 5-hydroxymethylfurans aldehyde.
The said reaction substrate of said step (1) is a hexose, can be to contain-the basic grape carbohydrate aldehyde radical hexose of CHO, and also can be the fructose class carbonyl hexose that contains C=O, like glucose, fructose, seminose, semi-lactosi, sorbose.
Solvent is water, ethanol, methyl alcohol, DMSO 99.8MIN., N in the said step (1), dinethylformamide, DMAC N,N, N; Dinethylformamide-halide salt system or N; N-N,N-DIMETHYLACETAMIDE-halide salt system is at N, in dinethylformamide-halide salt system; Halide salt and N, the mass ratio of dinethylformamide are (1: 30)-(1: 200); In DMAC N,N-halide salt system, the mass ratio of halide salt and DMAC N,N is (1: 30)-(1: 200).
Solvent is preferably DMSO 99.8MIN., N, dinethylformamide-lithiumbromide solvent system or DMAC N,N-sodium-chlor solvent system in the said step (1); At N, in dinethylformamide-lithiumbromide solvent system, lithiumbromide and N, the mass ratio of dinethylformamide are (1: 30)-(1: 200); In DMAC N,N-sodium-chlor solvent system, the mass ratio of sodium-chlor and DMAC N,N is (1: 30)-(1: 200).
In the ionic liquid that adds in the said step (1), positively charged ion is for replacing morpholine positively charged ion or substituted pyrrolidone positively charged ion; Negatively charged ion is cl ions, bromide anion, iodide ion, acetate ion, sulfate ion, hydrosulphuric acid radical ion, nitrate ion, phosphate anion, phosphoric acid hydrogen radical ion, dihydrogen phosphate ions, tetrafluoroborate ion, hexafluorophosphoricacid acid ions, to benzene methanesulfonic acid radical ion, methanesulfonate ions or trifluoromethanesulfonic acid radical ion.
In the ionic liquid in the said step (1), replacing morpholine positively charged ion or the cationic substituting group of substituted pyrrolidone is the alkyl of C1-C12, the thiazolinyl of C1-C12, the substituted alkyl of C1-C12 or the substituted alkenyl of C1-C12.
In the ionic liquid in the said step (1), said replacement morpholine positively charged ion or the cationic substituting group of substituted pyrrolidone are methyl, ethyl, propyl group, hexyl, octyl group, dodecyl, vinyl, propenyl, crotonyl cyclohexenyl, chloromethyl, bromotrifluoromethane, chlorobutyl, nitro methyl, ethylamino-, chloro vinyl, bromo propenyl or bromo cyclohexenyl.
In the said step (1), ion liquid add-on is preferably the 7.5-10% of reaction substrate mole number.
In the said step (2), under the protection of rare gas element, reacted 2-5 hour down at 80-110 ℃.
In the said step (2), rare gas element is nitrogen, argon gas or helium.
The ionic liquid that the present invention uses, general formula is following:
Positively charged ion is for replacing the morpholine positively charged ion in the formula (I); Substituent R
1Be the alkyl of C1-C12, the thiazolinyl of C1-C12, the substituted alkyl of C1-C12 or the substituted alkenyl of C1-C12, for example methyl, ethyl, propyl group, hexyl, octyl group, dodecyl, vinyl, propenyl, crotonyl cyclohexenyl, chloromethyl, bromotrifluoromethane, chlorobutyl, nitro methyl, ethylamino-, chloro vinyl, bromo propenyl or bromo cyclohexenyl; Negatively charged ion A
-For cl ions, bromide anion, iodide ion, acetate ion, sulfate ion, hydrosulphuric acid radical ion, nitrate ion, phosphate anion, phosphoric acid hydrogen radical ion, dihydrogen phosphate ions, tetrafluoroborate ion, hexafluorophosphoricacid acid ions, to benzene methanesulfonic acid radical ion, methanesulfonate ions or trifluoromethanesulfonic acid radical ion (referring to Chinese invention patent 200910070522.8; The applying date: on September 22nd, 2009; Open day on March 17th, 2010).
Positively charged ion is the substituted pyrrolidone positively charged ion in the formula (II); Substituent R
2Be the alkyl of C1-C12, the thiazolinyl of C1-C12, the substituted alkyl of C1-C12 or the substituted alkenyl of C1-C12, for example methyl, ethyl, propyl group, hexyl, octyl group, dodecyl, vinyl, propenyl, crotonyl cyclohexenyl, chloromethyl, bromotrifluoromethane, chlorobutyl, nitro methyl, ethylamino-, chloro vinyl, bromo propenyl or bromo cyclohexenyl; Negatively charged ion B
-For cl ions, bromide anion, iodide ion, acetate ion, sulfate ion, hydrosulphuric acid radical ion, nitrate ion, phosphate anion, phosphoric acid hydrogen radical ion, dihydrogen phosphate ions, tetrafluoroborate ion, hexafluorophosphoricacid acid ions, to benzene methanesulfonic acid radical ion, methanesulfonate ions or trifluoromethanesulfonic acid radical ion.
Intermediate ion liquid catalyst of the present invention is made up of N-methylmorpholine, pyrrolidone and sulfuric acid, the methylsulphonic acid of cheapness, and raw material is easy to get.Use acidic ion liquid as catalyzer among the present invention, can high-level efficiency, highly selective catalysis hexose prepares 5-hydroxymethylfurans aldehyde, follows dewatering cycle to produce at reaction process intermediate ion liquid, byproduct of reaction is a water, so little to the pollution of environment.Use ionic liquid to carry out catalyzed reaction simultaneously, can avoid the toxic effect of existing catalyzer, can avoid the use of high amounts of solvents and additive, make things convenient for the later separation purification process.In addition, the ionic liquid that uses is the catalytic quantity level, not only can separate purified product well, and can reach higher transformation efficiency.
Embodiment
Further specify technical scheme of the present invention below in conjunction with specific embodiment.
Embodiment 1
1.0g (5.6mmol) fructose is dissolved in the 10mL DMSO 99.8MIN., adds 0.56mmol N-methylmorpholine mesylate ionic liquid,, under the nitrogen protection, stir, react after 2 hours, with gas chromatograph-mass spectrometer and efficient liquid phase chromatographic analysis result at 90 ℃; The transformation efficiency of fructose is 91%, and the yield of 5-hydroxymethylfurans aldehyde can reach 74.8%; Can use saturated sodium bicarbonate neutralization reaction solution this moment, filter, and drying, product is collected in distillation.
Embodiment 2
1.0g (5.6mmol) fructose is dissolved in 10mLN, in dinethylformamide-Potassium Bromide (Potassium Bromide and N, the mass ratio of dinethylformamide are 1: 30); Add 0.42mmol N-Methyl pyrrolidone mesylate ionic liquid; At 90 ℃, under the argon shield, stir; React after 2 hours, with gas chromatograph-mass spectrometer and efficient liquid phase chromatographic analysis result; The transformation efficiency of fructose is 90%, and the yield of 5-hydroxymethylfurans aldehyde can reach 70.5%; Can use saturated sodium bicarbonate neutralization reaction solution this moment, filter, and drying, product is collected in distillation.
Embodiment 3
1.0g (5.6mmol) fructose is dissolved in 10mLN, in N-N,N-DIMETHYLACETAMIDE-lithium chloride (mass ratio of lithium chloride and DMAC N,N is 1: 200); Add 0.42mmolN-propyl pyrrole alkane ketone hydrosulphuric acid salt ion liquid; At 100 ℃, under the nitrogen protection, stir; React after 3 hours, with gas chromatograph-mass spectrometer and efficient liquid phase chromatographic analysis reaction result; The transformation efficiency of fructose is 93%, and the yield of 5-hydroxymethylfurans aldehyde can reach 71.4%; Can use saturated sodium bicarbonate neutralization reaction solution this moment, filter, and drying, product is collected in distillation.
Embodiment 4
1.0g (5.6mmol) fructose is dissolved in the 10ml water, adds 0.42mmol N-ethyl pyrrolidone mesylate ionic liquid,, under the nitrogen atmosphere, stir, react after 5 hours, with GC-MS and efficient liquid phase chromatographic analysis result at 80 ℃; The transformation efficiency of fructose is 72%, and the yield of 5-hydroxymethylfurans aldehyde can reach 51%; Can use saturated sodium bicarbonate neutralization reaction solution this moment, filter, and drying, product is collected in distillation.
Embodiment 5
1.0g (5.6mmol) fructose is dissolved in 10mLN, in dinethylformamide-lithiumbromide (lithiumbromide and N, the mass ratio of dinethylformamide are 1: 100); Add 0.42mmolN-SL 1332 mesylate ionic liquid; At 110 ℃, under the nitrogen protection, stir; React after 4 hours, with gas chromatograph-mass spectrometer and efficient liquid phase chromatographic analysis reaction result; The transformation efficiency of fructose is 97%, and the yield of 5-hydroxymethylfurans aldehyde can reach 78.5%; Can use saturated sodium bicarbonate neutralization reaction solution this moment, filter, and drying, product is collected in distillation.
Embodiment 6
1.0g (5.6mmol) glucose is dissolved in 10mL DMAC N,N-sodium-chlor (mass ratio of sodium-chlor and DMAC N,N is 1: 150); Add 0.42mmolN-SL 1332 hydrosulphuric acid salt ion liquid; At 90 ℃, under the air conservation, stir; React after 3 hours, with gas chromatograph-mass spectrometer and efficient liquid phase chromatographic analysis reaction result; Inversion rate of glucose is 79%, and the yield of 5-hydroxymethylfurans aldehyde can reach 52%; Can use saturated sodium bicarbonate neutralization reaction solution this moment, filter, and drying, product is collected in distillation.
Embodiment 7
1.0g (5.6mmol) glucose is dissolved in the 10ml water, adds 0.42mmolN-SL 1332 mesylate ionic liquid,, under the nitrogen protection, stir, react after 5 hours, with gas chromatograph-mass spectrometer and efficient liquid phase chromatographic analysis reaction result at 100 ℃; The transformation efficiency of glucose can reach 82.5%, the yield 47% of 5-hydroxymethylfurans aldehyde; Can use saturated sodium bicarbonate neutralization reaction solution this moment, filter, and drying, product is collected in distillation.
Embodiment 8
1.0g (5.6mmol) seminose is dissolved in 10mL DMAC N,N-lithium chloride (mass ratio of lithium chloride and DMAC N,N is 1: 80); Add 0.42mmolN-SL 1332 mesylate ionic liquid; At 100 ℃, under the helium atmosphere, stir; React after 3 hours, with gas chromatograph-mass spectrometer and efficient liquid phase chromatographic analysis reaction result; The transformation efficiency of glucose can reach 72.5%, and the yield of 5-hydroxymethylfurans aldehyde can reach 52%; Can use saturated sodium bicarbonate neutralization reaction solution this moment, filter, and drying, product is collected in distillation.
Embodiment 9
1.0g (5.6mmol) glucose is dissolved in the 10mL DMSO 99.8MIN., adds 0.56mmolN-methylmorpholine mesylate ionic liquids ionic liquids, at 110 ℃; Under the air atmosphere; Stir, react after 4 hours, with gas chromatograph-mass spectrometer and efficient liquid phase chromatographic analysis reaction result; The transformation efficiency of glucose can reach 70%, and the yield of 5-hydroxymethylfurans aldehyde is 55%; Can use saturated sodium bicarbonate neutralization reaction solution this moment, filter, and drying, product is collected in distillation.
Embodiment 10
1.0g (5.6mmol) glucose is dissolved in 10mLN, in the dinethylformamide solvent, adds 0.42mmolN-SL 1332 mesylate ionic liquid; At 110 ℃, under the argon atmosphere, stir; React after 2 hours, with gas chromatograph-mass spectrometer and efficient liquid phase chromatographic analysis reaction result; The transformation efficiency of glucose can reach 70.5%, and the yield of 5-hydroxymethylfurans aldehyde can reach 45.2%; Can use saturated sodium bicarbonate neutralization reaction solution this moment, filter, and drying, product is collected in distillation.
Embodiment 11
1.0g (5.6mmol) seminose is dissolved in 10mLN, in N-N,N-DIMETHYLACETAMIDE-sodium-chlor (mass ratio of sodium-chlor and DMAC N,N is 1: 100); Add 0.42mmolN-SL 1332 mesylate ionic liquid; At 100 ℃, under the air atmosphere, stir; React after 3 hours, with gas chromatograph-mass spectrometer and efficient liquid phase chromatographic analysis reaction result; The transformation efficiency of glucose can reach 82.5%, and the yield of 5-hydroxymethylfurans aldehyde can reach 61.4%; Can use saturated sodium bicarbonate neutralization reaction solution this moment, filter, and drying, product is collected in distillation.
Embodiment 12
1.0g (5.6mmol) semi-lactosi is dissolved in 10mL DMAC N,N-sodium-chlor (mass ratio of sodium-chlor and DMAC N,N is 1: 50); Add 0.42mmolN-SL 1332 mesylate ionic liquid; At 100 ℃, under the air atmosphere, stir; React after 3 hours, with gas chromatograph-mass spectrometer and efficient liquid phase chromatographic analysis reaction result; The transformation efficiency of glucose can reach 75.2%, and the yield of 5-hydroxymethylfurans aldehyde can reach 52%; Can use saturated sodium bicarbonate neutralization reaction solution this moment, filter, and drying, product is collected in distillation.
Embodiment 13
1.0g (5.6mmol) fructose is dissolved in 10mL N, in the dinethylformamide, adds 1.12mmolN-SL 1332 phosphate ion liquid; At 120 ℃, under the nitrogen atmosphere, stir; React after 3 hours, with gas chromatograph-mass spectrometer and efficient liquid phase chromatographic analysis reaction result; The transformation efficiency of fructose can reach 73.5%, and the yield of 5-hydroxymethylfurans aldehyde can reach 52%; With saturated sodium bicarbonate neutralization reaction solution, filter, drying, product is collected in distillation.
Embodiment 14
1.0g (5.6mmol) fructose is dissolved in 10mLN, in dinethylformamide-Potassium Bromide (Potassium Bromide and N, the mass ratio of dinethylformamide are 1: 30); Add 0.84mmolN-methylmorpholine tetrafluoroborate ion liquid; At 80 ℃, under the argon atmosphere, stir; React after 3 hours, with gas chromatograph-mass spectrometer and efficient liquid phase chromatographic analysis reaction result; The transformation efficiency of fructose can reach 62.4%, and the yield of 5-hydroxymethylfurans aldehyde can reach 42%; With saturated sodium bicarbonate neutralization reaction solution, filter, drying, product is collected in distillation.
Embodiment 15
1.0g (5.6mmol) sorbose is dissolved in the 10mL ethanol, adds the 0.28mmolN-vinyl pyrrolidone to benzene methanesulfonic acid salt ion liquid, at 70 ℃; Under the air atmosphere; Stir, react after 3 hours, with GC-MS and efficient liquid phase chromatographic analysis reaction result; The transformation efficiency of sorbose can reach 87.5%, and the yield of 5-hydroxymethylfurans aldehyde can reach 61%; With saturated sodium bicarbonate neutralization reaction solution, filter, drying, product is collected in distillation.
Embodiment 16
1.0g (5.6mmol) fructose is dissolved in 10mLN, in N-N,N-DIMETHYLACETAMIDE-sodium-chlor (mass ratio of sodium-chlor and DMAC N,N is 1: 200); Add 0.28mmolN-chloro vinyl pyrrolidone hexafluorophosphate ionic liquid; At 90 ℃, under the nitrogen atmosphere, stir; React after 3 hours, with gas chromatograph-mass spectrometer and efficient liquid phase chromatographic analysis reaction result; The transformation efficiency of fructose can reach 57.5%, and the yield of 5-hydroxymethylfurans aldehyde can reach 28%; With saturated sodium bicarbonate neutralization reaction solution, filter, drying, product is collected in distillation.
The catalytic dehydration of embodiment 17 seminoses
1.0g (5.6mmol) seminose is dissolved in the 10mL ethanol, adds 0.28mmolN-bromo propenyl pyrrolidone acetate ions liquid, at 90 ℃; Under the air atmosphere; Stir, react after 3 hours, with gas chromatograph-mass spectrometer and efficient liquid phase chromatographic analysis reaction result; The transformation efficiency of seminose can reach 74.9%, and the yield of 5-hydroxymethylfurans aldehyde can reach 52%; With saturated sodium bicarbonate neutralization reaction solution, filter, drying, product is collected in distillation.
Embodiment 18
1.0g (5.6mmol) fructose is dissolved in 10mLN, in N-N,N-DIMETHYLACETAMIDE-lithium chloride (mass ratio of lithium chloride and DMAC N,N is 1: 100); Add 0.28mmolN-chloromethyl pyrrolidone fluoroform sulphonate ionic liquid; At 80 ℃, under the helium atmosphere, stir; React after 2 hours, with gas chromatograph-mass spectrometer and efficient liquid phase chromatographic analysis reaction result; The transformation efficiency of fructose can reach 92.6%, and the yield of 5-hydroxymethylfurans aldehyde can reach 74%; With saturated sodium bicarbonate neutralization reaction solution, filter, drying, product is collected in distillation.
Above-mentioned instance shows, adopts the novel ionic liquid catalyst system that is provided among the present invention, and in suitable reaction medium, the condition that is provided according to invention can high-level efficiency, highly selective generates 5-hydroxymethylfurans aldehyde with the hexose catalytic dehydration.Reaction can be carried out in air atmosphere, also can under protection of inert gas such as nitrogen, carry out; Catalyst dissolution embodies the advantage and the effect of even phase catalyst fully in reaction system in reaction process, thereby reaction conditions is gentle; After entire reaction, catalyzer and substrate and product have than big difference, are easy to separate.In total reaction process, just fructose and the glucose compounds that are consumed; Production cost, cheap, product mainly is an oxygenatedchemicals, relatively more friendly to environment, reaction process is simple, can satisfy the requirement of Technological Economy.
More than the present invention has been done exemplary description; Should be noted that; Under the situation that does not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (5)
1. a method of utilizing ionic liquid-catalyzed generation 5 hydroxymethyl furfural is characterized in that, carries out according to following step:
(1) reaction substrate is dissolved in the solvent, adds ionic liquid again, said ion liquid add-on is the 5-20% of reaction substrate mole number;
(2) reacted at least 2 hours down at 70-120 ℃, can pass through neutralization reaction solution, filter, drying, distillation obtains 5-hydroxymethylfurans aldehyde;
The said reaction substrate of said step (1) is a hexose;
Solvent is water, ethanol, methyl alcohol, DMSO 99.8MIN., N in the said step (1), dinethylformamide, DMAC N,N, N; Dinethylformamide-halide salt system or N; N-N,N-DIMETHYLACETAMIDE-halide salt system is at N, in dinethylformamide-halide salt system; Halide salt and N, the mass ratio of dinethylformamide are (1: 30)-(1: 200); In DMAC N,N-halide salt system, the mass ratio of halide salt and DMAC N,N is (1: 30)-(1: 200);
In the ionic liquid that adds in the said step (1), positively charged ion is for replacing morpholine positively charged ion or substituted pyrrolidone positively charged ion; Negatively charged ion is cl ions, bromide anion, iodide ion, acetate ion, sulfate ion, hydrosulphuric acid radical ion, nitrate ion, phosphate anion, phosphoric acid hydrogen radical ion, dihydrogen phosphate ions, tetrafluoroborate ion, hexafluorophosphoricacid acid ions, to benzene methanesulfonic acid radical ion, methanesulfonate ions or trifluoromethanesulfonic acid radical ion; In the ionic liquid in the said step (1), replacing morpholine positively charged ion or the cationic substituting group of substituted pyrrolidone is chloro vinyl, bromo propenyl or chloromethyl.
2. a kind of method of utilizing ionic liquid-catalyzed generation 5 hydroxymethyl furfural according to claim 1 is characterized in that, the said reaction substrate of said step (1) is glucose, fructose, seminose, semi-lactosi or sorbose; Solvent is DMSO 99.8MIN., N in the said step (1), dinethylformamide-lithiumbromide solvent system or DMAC N,N-sodium-chlor solvent system; At N, in dinethylformamide-lithiumbromide solvent system, lithiumbromide and N, the mass ratio of dinethylformamide are (1: 30)-(1: 200); In DMAC N,N-sodium-chlor solvent system, the mass ratio of sodium-chlor and DMAC N,N is (1: 30)-(1: 200);
In the ionic liquid in the said step (1), said replacement morpholine positively charged ion or the cationic substituting group of substituted pyrrolidone are chloro vinyl, bromo propenyl or chloromethyl.
3. according to claim 1 or 2 described a kind of methods of utilizing ionic liquid-catalyzed generation 5 hydroxymethyl furfural, it is characterized in that in the said step (1), ion liquid add-on is the 7.5-10% of reaction substrate mole number.
4. according to claim 1 or 2 described a kind of methods of utilizing ionic liquid-catalyzed generation 5 hydroxymethyl furfural, it is characterized in that, in the said step (2), under the protection of rare gas element, reacted 2-5 hour down at 80-110 ℃.
5. a kind of method of utilizing ionic liquid-catalyzed generation 5 hydroxymethyl furfural according to claim 4 is characterized in that, in the said step (2), rare gas element is nitrogen, argon gas or helium.
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| CN102212048B (en) * | 2011-04-19 | 2013-08-21 | 天津理工大学 | Method for preparing hydroxymethyl furfural by catalytic dehydration reaction of hexose |
| US9162998B2 (en) | 2011-12-13 | 2015-10-20 | Basf Se | Preparation of 5-hydroxymethylfurfural (HMF) from saccharide solutions in the presence of a solvent having a boiling point greater than 60° C. and less than 200° C. (at standard pressure, called low boiler for short) |
| JP6073363B2 (en) * | 2011-12-13 | 2017-02-01 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Preparation of 5-hydroxymethylfurfural (HMF) from hexose solution in the presence of steam |
| JP6073364B2 (en) * | 2011-12-13 | 2017-02-01 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Preparation of 5-hydroxymethylfurfural (HMF) from a sugar solution in the presence of a solvent (abbreviated as low boiling solvent) having a boiling point (at standard pressure) above 60 ° C. and below 200 ° C. |
| CN102399203B (en) * | 2011-12-19 | 2014-05-07 | 浙江大学 | Method for preparing 5-hydroxymethylfurfural by degrading carbonhydrate through ionic liquid |
| EP2813494A1 (en) * | 2013-06-12 | 2014-12-17 | Basf Se | Method for the preparation of 5-hydroxymethylfurfural (HMF) |
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| 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 |
| CN104829562A (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 with additive |
| CN108997275A (en) * | 2018-06-20 | 2018-12-14 | 昆明理工大学 | A method of primary product distribution in control fructose-ethanol synthesis system |
| CN114805256B (en) * | 2022-05-17 | 2023-12-05 | 广东石油化工学院 | Method for preparing 5-hydroxymethylfurfural by catalyzing dehydration of fructosyl carbohydrate by using zwitterionic inner salt |
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