CN103172600A - Preparation method of furfuraldehyde - Google Patents
Preparation method of furfuraldehyde Download PDFInfo
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- CN103172600A CN103172600A CN2013101158427A CN201310115842A CN103172600A CN 103172600 A CN103172600 A CN 103172600A CN 2013101158427 A CN2013101158427 A CN 2013101158427A CN 201310115842 A CN201310115842 A CN 201310115842A CN 103172600 A CN103172600 A CN 103172600A
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Abstract
The invention discloses a preparation method of furfuraldehyde. The method comprises the following step of: on the basis of taking lignocelluloses biomass containing xylanunit as a raw material, reacting an ion liquid phase/organic phase dual-phase reaction system with the raw material taking aluminum chloride as a catalyst, wherein the ion liquid phase in the dual-phase reaction system is a choline chloride-adipic acid mixed solution, and the organic phase is methyl isobutyl ketone. The preparation method has the following advantages: in the preparation method, the ion liquid phase/organic phase dual-phase reaction system is adopted; steam is not consumed; no wastewater is discharged; the organic phase and the ion liquid phase can be recycled; the production energy consumption can be greatly reduced; the yield and selectivity of the furfuraldehyde are improved; the AlCl3.6H2O is used as the catalyst; the reaction speed can be quickened; the production cost is saved; corrosion of a reaction solution on equipment can be significantly reduced; the ion liquid adopted in the preparation method is environmental-friendly and cheap; the preparation process does not need other medium; and 100% of reaction quality efficiency can be achieved.
Description
Technical field
The present invention relates to the preparation method of the technology of preparing of basic organic chemical raw material, particularly a kind of furfural.
Background technology
Furfural is a kind of important basic organic chemical raw material, uses very extensively, and each chemical field constantly increases the demand of furfural.Furfural does not still have synthetic method at present, and industrial lignocellulose biomass hydrolysis by being rich in many contracting wood sugars makes.In world wide, the furfural production technology of main flow has Quaker Oats technique, Rosenlew technique, Petrole-chimie technique, Escher Wyss technique and Agrifuran technique.But there is more drawback in these techniques: 1) furaldehyde yield only has 50% left and right of theoretical value, the reaction times length, water, strong acid, high temperature, cause side reaction more with conditions such as oxygen contact, the selectivity of furfural is low; 2) steam consumption is large, can reach the 30-50 of furfural output doubly; 3) diluted acid is easily separated and recycle, and equipment corrosion is serious; 4) produce a large amount of acid furfural waste-waters, utmost point refractory reason.In a word, furfural production technology is demanded urgently improving.
Chinese scholars and technician have carried out more trial to the production technique of optimizing furfural.The process modification that improves the furfural productive rate concentrates on and improves temperature of reaction, increase strength of acid and Reaction time shorten.More representational have
Technology, this technology adopts adiabatic flash, and is capable of reducing energy consumption, improves productive rate and the purity of furfural.The another kind of main improvements of technique that have superiority are to improve temperature of reaction, Reaction time shorten, concrete grammar is after raw material is mixed acid, mixed solution to be added continuous tubular reactor, reacts 5-60s passing under the high temperature of saturation steam, 230-250 ℃, and this process recovery ratio can reach 70%.The novel process of Karl J.Zeitsch exploitation adopts tubular reactor, and the adjusting by reactor pressure makes furfural can in time enter vapour phase, can significantly reduce energy consumption, improves productive rate.The contribution aspect reduction furfural production energy consumption of the patent of Dai Er volt Polytechnics is outstanding, and the principal feature of this technology is the aqueous solution and the steam countercurrent flow that makes furfural, and energy-saving effect is fairly obvious.More than improving one's methods focuses on the control of carrying out the process optimization aspect, has certain effect to improving productive rate and reducing energy consumption, but there is no thoroughly to solve the problem of energy consumption and acid waste water.
Given this, thoroughly solve the problems of furfural production, can not only depend on local optimization and improvement, must overturn to the production of furfural the improvement of formula, emphasis is the catalysts and solvents system that will develop green Cheap highly effective.
Summary of the invention
The objective of the invention is provides a kind of preparation method of furfural for above-mentioned technical Analysis and existing problems, and the method new technology can solve from the source problem of acid waste water furfural production.
Technical scheme of the present invention:
A kind of preparation method of furfural, take the lignocellulose biomass that is rich in many contracting wood sugars as raw material, adopt ionic liquid phase/organic phase biphasic reaction system, biphasic reaction system intermediate ion liquid phase (IL) is choline chloride 60-hexanodioic acid mixed solution, organic phase is methyl iso-butyl ketone (MIBK) (MIBK), with AlCl
36H
2O is that catalyzer and raw material react preparation, and step is as follows:
1) choline chloride 60 and hexanodioic acid are mixed, the mol ratio of choline chloride 60 and hexanodioic acid is 1:1, obtains homogeneous liquid 100 ℃ of lower heated and stirred, then 80 ℃ of lower vacuum-dryings, makes choline chloride 60-hexanodioic acid mixed solution;
2) with raw material, choline chloride 60-hexanodioic acid mixed solution, MIBK and the catalyst A lCl of drying
36H
2React in the autoclave that O adds band to stir, temperature of reaction is 160 ℃, and pressure is 5Mpa, and the reaction times is 1h, obtains reaction solution;
3) organic phase in reaction solution and ionic liquid are separated, organic phase is the mixture of MIBK and furfural, and ionic liquid reaches the catalyst A lCl that is dissolved in wherein mutually
36H
2The O recycling use;
4) mixture distillation with MIBK and furfural separates, and wherein under 0.01MPa, 50 ℃, the gained cut is MIBK, is furfural, the MIBK recycling use at 0.01MPa, 95 ℃ of lower gained cuts.
Described raw material is the mixture of one or more arbitrary proportions in wood sugar, wood sugar oligopolymer and wood sugar polymer.
The raw material of described drying, choline chloride 60-hexanodioic acid mixed solution, MIBK and catalyst A lCl
36H
2The amount ratio of O is 40mg:2ml:4ml:5mg.
Advantage of the present invention is: this preparation method adopts ionic liquid phase/organic phase diphasic system, does not consume steam, non-wastewater discharge, and organic phase all can be recycled mutually with ionic liquid, can significantly reduce production energy consumption, improves productive rate and the selectivity of furfural; Use AlCl
36H
2O is catalyzer, can accelerate speed of reaction, saves production cost, and can significantly reduce reaction soln to the corrosion of equipment; The ionic liquid that adopts in this preparation method is green cheap, and its preparation process does not need other media, and can reach 100% reaction mass efficient; But ionic liquid phase choline chloride 60-hexanodioic acid and organic phase MIBK all reuse recycle.
Description of drawings
Accompanying drawing is this preparation method's process flow diagram.
Specific embodiments
Embodiment 1:
A kind of preparation method of furfural, as shown in drawings, take wood sugar as raw material, adopt ionic liquid phase/organic phase biphasic reaction system, biphasic reaction system intermediate ion liquid phase (IL) is choline chloride 60-hexanodioic acid mixed solution, and organic phase is methyl iso-butyl ketone (MIBK) (MIBK), with AlCl
36H
2O is that catalyzer and raw material react preparation, and step is as follows:
1) choline chloride 60 and hexanodioic acid are mixed, the mol ratio of choline chloride 60 and hexanodioic acid is 1:1, obtains homogeneous liquid 100 ℃ of lower heated and stirred, then 80 ℃ of lower vacuum-dryings, makes choline chloride 60-hexanodioic acid mixed solution;
2) with 400mg wood sugar, 20ml choline chloride 60-hexanodioic acid mixed solution, 40ml MIBK and 50mg catalyst A lCl
36H
2O adds autoclave and under agitation reacts, and temperature of reaction is 160 ℃, and pressure is 5Mpa, and the reaction times is 1h, obtains reaction solution;
3) organic phase in reaction solution and ionic liquid are separated, organic phase is the mixture of MIBK and furfural, and ionic liquid reaches the catalyst A lCl that is dissolved in wherein mutually
36H
2The O recycling use;
4) mixture distillation with MIBK and furfural separates, and wherein under 0.01MPa, 50 ℃, the gained cut is MIBK, is furfural, the MIBK recycling use at 0.01MPa, 95 ℃ of lower gained cuts.
The furfural productive rate is: in organic phase the furfural productive rate be 73.4%, IL mutually in the furfural productive rate be 12.2%, the furfural overall yield is 85.6%, percentage extraction is 85.7%.
Embodiment 2:
A kind of preparation method of furfural take xylan as raw material, adopts ionic liquid phase/organic phase biphasic reaction system, and biphasic reaction system intermediate ion liquid phase (IL) is choline chloride 60-hexanodioic acid mixed solution, and organic phase is methyl iso-butyl ketone (MIBK) (MIBK), with AlCl
36H
2O is that catalyzer and raw material react preparation, and preparation process is identical with embodiment 1.
The furfural productive rate is: in organic phase the furfural productive rate be 70.8%, IL mutually in the furfural productive rate be 11.3%, the furfural overall yield is 82.1%, percentage extraction is 86.2%.
Claims (3)
1. the preparation method of a furfural, it is characterized in that: take the lignocellulose biomass that is rich in many contracting wood sugars as raw material, adopt ionic liquid phase/organic phase biphasic reaction system, biphasic reaction system intermediate ion liquid phase (IL) is choline chloride 60-hexanodioic acid mixed solution, organic phase is methyl iso-butyl ketone (MIBK) (MIBK), with AlCl
36H
2O is that catalyzer and raw material react preparation, and step is as follows:
1) choline chloride 60 and hexanodioic acid are mixed, the mol ratio of choline chloride 60 and hexanodioic acid is 1:1, obtains homogeneous liquid 100 ℃ of lower heated and stirred, then 80 ℃ of lower vacuum-dryings, makes choline chloride 60-hexanodioic acid mixed solution;
2) with raw material, choline chloride 60-hexanodioic acid mixed solution, MIBK and the catalyst A lCl of drying
36H
2React in the autoclave that O adds band to stir, temperature of reaction is 160 ℃, and pressure is 5Mpa, and the reaction times is 1h, obtains reaction solution;
3) organic phase in reaction solution and ionic liquid are separated, organic phase is the mixture of MIBK and furfural, and ionic liquid reaches the catalyst A lCl that is dissolved in wherein mutually
36H
2The O recycling use;
4) mixture distillation with MIBK and furfural separates, and wherein under 0.01MPa, 50 ℃, the gained cut is MIBK, is furfural, the MIBK recycling use at 0.01MPa, 95 ℃ of lower gained cuts.
2. the preparation method of furfural according to claim 1, it is characterized in that: described raw material is the mixture of one or more arbitrary proportions in wood sugar, wood sugar oligopolymer and wood sugar polymer.
3. the preparation method of furfural according to claim 1, is characterized in that: the raw material of described drying, choline chloride 60-hexanodioic acid mixed solution, MIBK and catalyst A lCl
36H
2The amount ratio of O is 40mg:2ml:4ml:5mg.
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| CN2013101158427A CN103172600A (en) | 2013-04-03 | 2013-04-03 | Preparation method of furfuraldehyde |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613573A (en) * | 2013-11-11 | 2014-03-05 | 河南师范大学 | Method for synthesizing coumarin and derivatives thereof under catalysis of choline ionic liquids |
| CN104072450A (en) * | 2014-07-14 | 2014-10-01 | 南京林业大学 | Novel method for preparing 5-hydroxymethylfurfural and furfural by adopting biomass raw material |
| CN109651307A (en) * | 2019-01-16 | 2019-04-19 | 中国科学院广州能源研究所 | A kind of method that fiber-like Chinese medicine slag prepares furan derivatives |
| CN112552266A (en) * | 2020-12-18 | 2021-03-26 | 安徽工业大学 | Method for preparing furfural by extracting hemicellulose from alkali liquor |
| CN115707694A (en) * | 2021-08-18 | 2023-02-21 | 中国石油化工股份有限公司 | Preparation method of furfural |
| CN116943743A (en) * | 2023-07-23 | 2023-10-27 | 浙江华康药业股份有限公司 | Double-acid catalyst and method for preparing furfural by catalyzing hemicellulose or xylose |
Citations (2)
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| CN102491304A (en) * | 2011-12-02 | 2012-06-13 | 罗绍华 | Method for preparing lithium iron phosphate in ionic eutectic mixture |
| CN102887878A (en) * | 2011-07-21 | 2013-01-23 | 财团法人工业技术研究院 | Preparation method of furfural compound and mixed solution for preparing same |
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2013
- 2013-04-03 CN CN2013101158427A patent/CN103172600A/en active Pending
Patent Citations (2)
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| CN102887878A (en) * | 2011-07-21 | 2013-01-23 | 财团法人工业技术研究院 | Preparation method of furfural compound and mixed solution for preparing same |
| CN102491304A (en) * | 2011-12-02 | 2012-06-13 | 罗绍华 | Method for preparing lithium iron phosphate in ionic eutectic mixture |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613573A (en) * | 2013-11-11 | 2014-03-05 | 河南师范大学 | Method for synthesizing coumarin and derivatives thereof under catalysis of choline ionic liquids |
| CN103613573B (en) * | 2013-11-11 | 2015-06-17 | 河南师范大学 | Method for synthesizing coumarin and derivatives thereof under catalysis of choline ionic liquids |
| CN104072450A (en) * | 2014-07-14 | 2014-10-01 | 南京林业大学 | Novel method for preparing 5-hydroxymethylfurfural and furfural by adopting biomass raw material |
| CN104072450B (en) * | 2014-07-14 | 2016-03-02 | 南京林业大学 | Biomass material prepares the novel method of 5 hydroxymethyl furfural and furfural |
| CN109651307A (en) * | 2019-01-16 | 2019-04-19 | 中国科学院广州能源研究所 | A kind of method that fiber-like Chinese medicine slag prepares furan derivatives |
| CN112552266A (en) * | 2020-12-18 | 2021-03-26 | 安徽工业大学 | Method for preparing furfural by extracting hemicellulose from alkali liquor |
| CN115707694A (en) * | 2021-08-18 | 2023-02-21 | 中国石油化工股份有限公司 | Preparation method of furfural |
| CN115707694B (en) * | 2021-08-18 | 2024-03-12 | 中国石油化工股份有限公司 | Preparation method of furfural |
| CN116943743A (en) * | 2023-07-23 | 2023-10-27 | 浙江华康药业股份有限公司 | Double-acid catalyst and method for preparing furfural by catalyzing hemicellulose or xylose |
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Application publication date: 20130626 |