CN105175366A - Method for producing 2,5-dimethyl furan (2,5-DMF) by fructose one-step process - Google Patents

Method for producing 2,5-dimethyl furan (2,5-DMF) by fructose one-step process Download PDF

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CN105175366A
CN105175366A CN201510573519.3A CN201510573519A CN105175366A CN 105175366 A CN105175366 A CN 105175366A CN 201510573519 A CN201510573519 A CN 201510573519A CN 105175366 A CN105175366 A CN 105175366A
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fructose
dmf
dimethyl furan
step production
hmf
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CN105175366B (en
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魏作君
楼炯涛
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Zhejiang University ZJU
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Zhejiang University ZJU
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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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Furan Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention discloses a method for producing 2,5-dimethyl furan (2,5-DMF) by a fructose one-step process. The method comprises the following steps: reacting under the conditions of 140 to 220 DEG C, 400 to1000rpm (revolutions per minute) and 0.5 to 4MPa by taking fructose as a raw materials, Ru/C and mixed liquid of AlCl3 and inorganic acid as catalysts and N,N-dimethylformamide as solvent; after reaction is ended, performing suction filtration on reaction liquid, and recovering Ru/C from a filter cake; performing aftertreatment on filtrate to obtain the product 2,5-dimethyl furan. According to the method disclosed by the invention, 2,5-DMF is produced from the fructose, which is wider in source and lower in price, instead of 5-HMF (5-hydroxymethylfurfural); the method has greater industrial application value; the course of the original two-step process is integrated into one step, therefore the problem that the intermediate product 5-HMF is difficult to separate can be effectively solved; the method has obvious innovation and simple and easy experiment operations; good 2,5-DMF yield can be obtained, and the molar yield reaches 66.3 percent.

Description

One is by the method for fructose One-step production 2,5-dimethyl furan
(1) technical field
The present invention relates to the method that one prepares 2,5-dimethyl furan (2,5-DMF), particularly one take fructose as starting raw material, and with Ru/C and Louis-bronsted mixing acid for catalyzer, single stage method prepares the method for 2,5-DMF.
(2) background technology
Platform chemicals 5 hydroxymethyl furfural (5-HMF) hydrogenolysis obtained with carbohydrate inversion prepare 2,5-DMF, be considered to renewable bioenergy most with prospects at present.Compared with the traditional biomass energy-ethanol, 2,5-DMF has higher boiling point (92-94 DEG C of vs.78.4 DEG C), and higher octane value (119vs.111), more easily mixes with gasoline, higher energy density (31.5kJcm -3vs.23kJcm -3).Meanwhile, the lower (0.30kJcm of the steam latent heat of 2,5-DMF -3vs.0.71kJcm -3), the energy spent by rectification and purification is lower.
The main method of producing 2,5-DMF is with metal carrying catalyst, catalysis 5-HMF hydrogenolysis (US2011263880A1,2011; CN101434588A, 2012), but being converted from biomass energy, best circumstance is more easy to get, and more easily circulates, and more cheap hydrocarbon polymer replaces 5-HMF, as the starting raw material of production 2,5-DMF.From hydrocarbon polymer to 2,5-DMF, comprise two steps.The first step is, hydrocarbon polymer is under Lewis acid or bronsted acid catalysis, and dehydration obtains 5-HMF; Second step is that metal catalyst catalysis 5-HMF hydrogenolysis is converted into 2,5-DMF.Although obtaining 2,5-DMF from 5-HMF has very high yield, from hydrocarbon polymer, be separated 5-HMF very difficult.Therefore it is very poor with hydrocarbon polymer to be that starting raw material produces the selectivity of 2,5-DMF.
Dumesic and Binder (CN102066304A, 2011) obtains 2,5-DMF from untreated maize straw, first, with CrCl 3at HCl, N, N, in-dimethyl formamide (DMF) and LiCl mixed system, at 140 DEG C, catalyse cellulose dehydration, obtains the 5-HMF yield of 48mol%, then uses Cu-Ru catalysis 5-HMF hydrogenolysis after 2h, react 10h at 220 DEG C, finally only obtain 2, the 5-DMF yields of 9mol%.(the CN103864732A such as Zhang Tao, 2014) be that reaction substrate prepares 2 with fructose, 5-DMF, first by fructose, Ru/C catalyzer and ionic liquid BminCl add reactor, at 130 DEG C, heat 30min, are adding tetrahydrofuran (THF) (THF), 2, the 5-DMF yields that 5h obtains 40.8mol% are reacted at 5MPa hydrogen pressure and 220 DEG C.Wu Tinghua etc. (CN102417493A, 2012) are reaction substrate with glucose, adopt single stage method to prepare 2,5-DMF, add glucose sugar in a kettle., solvent, n-butanol, the PO of reduction at 325 DEG C x-Mo 2o 3-Ru/CNTs catalyzer, reacts 4h at 1.2MPa hydrogen pressure and 240 DEG C, obtains 2, the 5-DMF yields of 90mol%.Saha reports with ZnCl 2-Pd/C is the technique of catalyzer, One-step production 2,5-DMF, and yield only has 22mol%; In same system, if be raw material with 5-HMF, then can obtain 2,5-DMF very high yields.
Applicant has found that one is at Louis-bronsted mixing acid, take DMF as solvent, from the method for fructose High-efficient Production 5-HMF.In order to simplify reactions steps, avoid complicated purification process, it is a kind of by fructose single stage method that applicant attempts exploitation, through dehydration, hydrogenolysis, obtains the technique of 2,5-DMF of high yield.
(3) summary of the invention
The object of the invention is to provide one in one pot from fructose High-efficient Production 2, the technique of 5-DMF, the method overcome in conventional two-step, intermediate product 5-HMF is difficult to the shortcoming of separating-purifying, and raw material is easy to get, and 2, the total recovery of 5-DMF is up to 66.3mol%, fructose converting rate is greater than 99%, is the highest yield be in the news at present, has higher industrial using value.
The technical solution used in the present invention is:
The invention provides a kind of method by fructose One-step production 2,5-dimethyl furan, described method is: be raw material with fructose, with Ru/C and AlCl 3and mineral acid mixed solution is catalyzer, take DMF as solvent, 140 ~ 220 DEG C, 400 ~ 1000rpm, to react, after reacting completely, by reaction solution suction filtration under 0.5 ~ 4MPa condition, filter cake reclaims Ru/C, and filtrate obtains product 2,5-dimethyl furan through aftertreatment; Described fructose and Ru/C mass ratio are 1:0.05 ~ 0.5, and described mineral acid is H 2sO 4and H 3pO 4in one or both, described AlCl 3, mineral acid is 0.1 ~ 0.5:0.5 ~ 2:10 with the ratio of the amount of substance of fructose, preferred described AlCl 3, H 2sO 4, H 3pO 4be 0.1 ~ 0.5:0 ~ 2:0 ~ 2:10 with the ratio of the amount of substance of fructose, described DMF volumetric usage counts 20 ~ 60ml/g with fructose quality.
Further, described reaction be 200 DEG C, carry out under 600rpm, 1.5MPa condition.
Further, described fructose and Ru/C mass ratio are 1:0.2.
Further, described Ru/C is with metal Ru for active ingredient, is the catalyzer that carrier is prepared through the precipitator method with gac, and in Ru/C, the mass loading amount of Ru is 1 ~ 5wt%, preferred 5wt%.
Further, described mineral acid is H 2sO 4and H 3pO 4, described AlCl 3, H 2sO 4, H 3pO 4be 0.25:0.7:1:10 with the ratio of the amount of substance of fructose.
Further, described DMF volumetric usage counts 33ml/g with fructose quality.
Further, described filtrate is in filtrate, add several zeolites through the method for aftertreatment, at 96 DEG C, carries out distillation operation, obtain colourless oil liquid under condition of normal pressure, gas chromatographic detection its be 2,5-DMF.
Compared with prior art, beneficial effect of the present invention is mainly reflected in:
(1) the present invention source is more extensive, the fructose that price is more cheap replaces 5-HMF to produce 2,5-DMF, its industrial application value is larger, by the process conformity of original two-step approach in a step, effectively can solve the problem of intermediate product 5-HMF separation difficulty, there is obvious novelty, experimental implementation is simple, can obtain good 2,5-DMF yields (66.3mol%).
(2) in reaction system of the present invention, the reusing that Ru/C catalyzer used has had, reuse through 3 times, the yield of 2,5-DMF does not all significantly reduce.
(4) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
In embodiment of the present invention Ru/C used, the mass loading amount of Ru is 5%, and purchased from space auspicious (Shanghai) Chemical Co., Ltd., described mol% refers to mole percent concentration.
Embodiment 1 fructose One-step production 2,5-DMF
Experiment is carry out in the steel high-pressure reactor of 100mL at a volume, and raw material fructose consumption is 1.8g (10mmol), weighs catalyzer Ru/C, AlCl 3, H 2sO 4, H 3pO 4consumption be respectively 0.2g, 0.056g (0.42mmol), 0.098g (1mmol), 0.147g (1.5mmol), solvent DMF consumption 60mL, control rotating speed 600rpm, hydrogen pressure 1.5MPa, temperature of reaction 200 DEG C, reaction 12h, after reaction terminates, direct sampling, adopt HPLC and gas chromatographic detection, reaction solution suction filtration, filter cake reclaims Ru/C, Ru/C DMF washes clean, recycle, several zeolites are added in filtrate, at 96 DEG C, distillation operation is carried out under condition of normal pressure, obtain colourless oil liquid, detect analysis and obtain 2, 5-DMF yield is 58.5mol%, fructose converting rate >99mol%.
Fructose is analyzed by high performance liquid chromatography (HPLC): detector: Waters410 Differential Refractometer; hPX-87H9 μm of post, 300 × 7.8mm; With 5mmoll -1h 2sO 4ultrapure water solution is moving phase, flow velocity 0.6mlmin -1, column temperature 60 DEG C.
Gas-chromatography detection method: detect and carry out, with N on gas chromatograph (Agilent7890) 2for carrier gas, hydrogen flame ionization detector detects, nonpolar capillary column (HP-5,30m × 0.32mm × 0.25 μm), sample size 0.4 μ L, temperature in 250 DEG C, detector temperature 260 DEG C, splitting ratio 1:10, column temperature adopts programmed temperature method, and (initial temperature 100 DEG C, with 5 DEG C of min -1speed rise to 250 DEG C, and this temperature retain 10min), be internal standard substance with dodecane, use inner mark method ration.
Embodiment 2-12
With reference to test conditions described in table 1, adopt embodiment 1 method to carry out fructose single stage method and prepare 2,5-DMF, the results are shown in Table shown in 1.
Table 1 embodiment 2-12 test conditions and result
Embodiment 13-15
According to test conditions described in table 2, adopt method described in embodiment 1, test with the Ru/C that embodiment 15 reclaims, test conditions and the results are shown in Table shown in 2.
Table 2Ru/C recycles situation
Comparative example 1 is that raw material two-step approach prepares 2,5-DMF with fructose
Experiment is carry out in the steel high-pressure reactor of 100mL at a volume, and raw material fructose consumption is 1.8g, catalyst A lCl 3, H 2sO 4, H 3pO 4consumption be respectively 0.033g, 0.069g, 0.098g, solvent DMF consumption 60mL, reacts 20min at 120 DEG C, then adds the acid in 0.1g sodium carbonate removing system, drop into 0.2gRu/C, control rotating speed 600rpm, hydrogen pressure 1.5MPa, temperature of reaction 200 DEG C, reaction 12h, after reaction terminates, direct sampling detect, product detection method with embodiment 1,2,5-DMF yield is 40.2mol%, fructose converting rate >99mol%.Under similar conditions, the optimal yield that can obtain 5-HMF is 92.6mol% to the fructose hydrolysis reaction of the first step, and fructose converting rate is 99.9mol%.Under experimental conditions, to obtain 5-HMF transformation efficiency be 100mol%, 2,5-DMF yield is 93.9mol% to the hydrogenolysis of second step 5-HMF.If be simply multiplied, the total recovery of 2,5-DMF is to I haven't seen you for ages more than 80mol%, but the 5-HMF separating-purifying that the first step is obtained by reacting is very complicated, can cause a large amount of losses of 5-HMF, therefore 2, the 5-DMF yields that two-step approach obtains are very low.
Comparative example 2 is catalysis fructose One-step production 2,5-DMF under no acidic catalyzer
Experiment is carry out in the steel high-pressure reactor of 100mL at a volume, and raw material fructose consumption is 1.8g, and weighing catalyzer Ru/C consumption is 0.2g, solvent DMF consumption 60mL, controls rotating speed 600rpm, hydrogen pressure 1.5MPa, temperature of reaction 200 DEG C, reaction 12h, after reaction terminates, direct sampling detects, product detection method is with embodiment 1,2,5-DMF yield is 35.1mol%, fructose converting rate >99mol%.
More known by the embodiment of the present invention and comparative example: add the generation that Lewis acid is conducive to 2,5-DMF in hydrogenation catalyst system, because Lewis acid can prevent the polymerization of intermediate product 5-HMF.Fructose One-step production 2,5-DMF, its experiment operating process is simple, not only solves the difficult problem that intermediate product 5-HMF is separated, can also improve the yield of final product 2,5-DMF.In hydrogenation catalyst system, add mixing acid, 2,5-DMF best yields can be obtained under suitable proportion.

Claims (7)

1. one kind by the method for fructose One-step production 2,5-dimethyl furan, it is characterized in that described method is: be raw material with fructose, with Ru/C and AlCl 3and mineral acid mixed solution is catalyzer, take DMF as solvent, 140 ~ 220 DEG C, 400 ~ 1000rpm, to react, after reacting completely, by reaction solution suction filtration under 0.5 ~ 4MPa condition, filter cake reclaims Ru/C, and filtrate obtains product 2,5-dimethyl furan through aftertreatment; Described fructose and Ru/C mass ratio are 1:0.05 ~ 0.5, and described mineral acid is H 2sO 4and H 3pO 4in one or both, described AlCl 3, mineral acid is 0.1 ~ 0.5:0.5 ~ 2:10 with the ratio of the amount of substance of fructose, described DMF volumetric usage counts 20 ~ 60ml/g with fructose quality.
2. as claimed in claim 1 by the method for fructose One-step production 2,5-dimethyl furan, it is characterized in that described reaction be 200 DEG C, carry out under 600rpm, 1.5MPa condition.
3., as claimed in claim 1 by the method for fructose One-step production 2,5-dimethyl furan, it is characterized in that described fructose and Ru/C mass ratio are 1:0.2.
4., as claimed in claim 1 by the method for fructose One-step production 2,5-dimethyl furan, it is characterized in that the mass loading amount of Ru in described Ru/C is 1 ~ 5wt%.
5., as claimed in claim 1 by the method for fructose One-step production 2,5-dimethyl furan, it is characterized in that described mineral acid is H 2sO 4and H 3pO 4, described AlCl 3, H 2sO 4, H 3pO 4be 0.25:0.7:1:10 with the ratio of the amount of substance of fructose.
6., as claimed in claim 1 by the method for fructose One-step production 2,5-dimethyl furan, it is characterized in that described DMF volumetric usage counts 33ml/g with fructose quality.
7., as claimed in claim 1 by the method for fructose One-step production 2,5-dimethyl furan, it is characterized in that described filtrate through the method for aftertreatment is, in filtrate, add zeolite, at 96 DEG C, under condition of normal pressure, carry out rectifying, obtain colourless oil liquid, be 2,5-dimethyl furan.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106496165A (en) * 2016-10-31 2017-03-15 中国科学院过程工程研究所 A kind of method of catalyzed conversion furfural

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CN101434588B (en) * 2007-11-14 2011-08-10 中国科学院大连化学物理研究所 Method for preparing 2,5-dimethyl furan from 5-hydroxymethyl furfural
CN103864732A (en) * 2012-12-18 2014-06-18 中国科学院大连化学物理研究所 Method for preparing 2,5-dimethyl furan by use of fructosyl biomass

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106496165A (en) * 2016-10-31 2017-03-15 中国科学院过程工程研究所 A kind of method of catalyzed conversion furfural
CN106496165B (en) * 2016-10-31 2018-11-20 中国科学院过程工程研究所 A kind of method of catalyzed conversion furfural

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