CN103554068B - The method of furfural prepared by a kind of vapor phase acid and Lewis acid altogether catalytic hydrolysis - Google Patents
The method of furfural prepared by a kind of vapor phase acid and Lewis acid altogether catalytic hydrolysis Download PDFInfo
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- CN103554068B CN103554068B CN201310576072.6A CN201310576072A CN103554068B CN 103554068 B CN103554068 B CN 103554068B CN 201310576072 A CN201310576072 A CN 201310576072A CN 103554068 B CN103554068 B CN 103554068B
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- furfural
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- lewis acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
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- Organic Chemistry (AREA)
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to technical field of preparation of furaldehyde, be specifically related to a kind of method adopting vapor phase acid and the common catalytic hydrolysis of Lewis acid to prepare furfural.The method be by biomass material and Lewis acid aqueous solution even, be placed in tubular reactor, pass into nitrogen purge, then pass into the hydrochloric acid vapour of vaporization from one end of tubular reactor, collect phlegma from the other end of tubular reactor, phlegma is furfural crude product.The present invention adds Lewis acid promoter, improves furaldehyde yield, avoids the corrosion to equipment simultaneously, without any acid waste liquid discharge, avoids environmental pollution.
Description
Technical field
The invention belongs to technical field of preparation of furaldehyde, be specifically related to a kind of method adopting vapor phase acid and the common catalytic hydrolysis of Lewis acid to prepare furfural.
Background technology
Furfural is hydrolyzed generation pentose under the action of an acid by piperylene, then formed by dehydration of pentoses cyclisation.Stripping, solvent extraction etc. can be taked in the production process of furfural to operate the furfural of generation is shifted out in time from system.In the last few years, people developed supercritical CO
2the novel method of furfural is shifted out Deng extraction.The method of producing furfural at present in the world has sulfuric acid process, method of acetic acid, hydrochloric acid method, inorganic salt method.Furfural production factory more than 95% of China adopts sulfuric acid catalysis method, and minority producer uses hydrochloric acid method.Sulfuric acid process is classical furfural production method, makes catalyzer, by raw material and catalyzer boiling under elevated pressure with the dilute sulphuric acid of 3% ~ 6%, take reactant out of with high pressure or superheated vapour, obtain furfural finished product after fractionation, this method adopts periodical operation, energy consumption is high, and the byproduct rate of recovery is low, and cost is high.Byproduct acetic acid in method of acetic acid furfural production process is catalyzer, produces furfural at high temperature under high pressure, and the furfural purity that this method is produced is high, and byproduct is also now widely used acetic acid, and in addition, technological process is simple.Hydrochloric acid method uses hydrochloric acid to prepare the method for furfural for catalyzer hydrolysis at ambient pressure, and raw material availability is high, and product yield is high, and quality is good, but technical process is long, and operation control system is complicated, and greatly, corrodibility is comparatively serious for investment of production.Inorganic salt method is mainly the method that furfural is prepared in catalyzer hydrolysis with superphosphate, and this method hydrolytic residue itself is a kind of good composite fertilizer, and output is high, and equipment corrosion is little, but inorganic salt catalytic activity is lower, becomes the product cycle longer.
The biomass such as corn cob, stalk, rice husk have wide prospect as the raw material producing furfural.Along with the development of furfurol industry, development furfural production novel process, the Mierocrystalline cellulose in separate raw materials and hemicellulose are also used, and are the inevitable development trend of furfurol industry.
Summary of the invention
The method of furfural prepared by the employing vapor phase acid that the object of the present invention is to provide a kind of yield higher and Lewis acid altogether catalytic hydrolysis.
The present invention is by the following technical solutions:
The method of furfural prepared by a kind of vapor phase acid and Lewis acid altogether catalytic hydrolysis, by biomass material and Lewis acid aqueous solution even, be placed in tubular reactor, pass into nitrogen purge, then the hydrochloric acid vapour of vaporization is passed into from one end of tubular reactor, collect phlegma from the other end of tubular reactor, phlegma is furfural crude product.
The temperature of described tubular reactor controls at 155-180 DEG C.
Lewis acidic consumption is the 1-5% of biomass material quality, and the mass concentration of the Lewis acid aqueous solution is 1.5-8%.
Further preferably, the mass concentration of the Lewis acid aqueous solution is 4.5-7.5%.
Lewis acid is FeCl
3, AlCl
3, ZnCl
2or CuCl
2, preferred FeCl
3.
The mass concentration of hydrochloric acid vapour is 0.5-3%.
Biomass material comprises corn cob, maize straw, wheat stalk, rice husk, Pericarppium arachidis hypogaeae etc.
The present invention is compared with existing furfural production technology, and its feature, advantage and positively effect are mainly reflected in the following aspects:
One is react to carry out at ambient pressure, and temperature of reaction is more than the dew point of hydrochloric acid, avoids the corrosion to equipment, adds Lewis acid promoter, improve furaldehyde yield;
Two is that vapor phase acid (hydrochloric acid vapour) catalyzer that reaction adopts can reclaim and recycle completely, without any acid waste liquid discharge, avoids the problems such as environmental pollution.
Embodiment
Below provide several embodiment, the present invention is described in detail.
Embodiment 1:
Take 300g corn cob, take the FeCl of 12g
3be made into the aqueous solution of 200g, by biomass material and FeCl
3solution mixes, be placed in tubular reactor, tubular reactor adopts oil bath heating, controls tubular type temperature of reaction at 155 DEG C, then passes into nitrogen emptying air, pass into the concentration after vaporization is 1% hydrochloric acid vapour simultaneously, hydrochloric acid vapour passes into above reactor, and below out rear condensation is collected, and the concentration of gas chromatographic detection furfural is 14.03g/L, calculating furfural ultimate production is 46.03g, and furaldehyde yield is 76.34%.
Embodiment 2:
Take 300g corn cob, take the FeCl of 4g
3be made into the aqueous solution of 150g, by biomass material and FeCl
3solution mixes, be placed in tubular reactor, tubular reactor adopts oil bath heating, controls tubular type temperature of reaction at 170 DEG C, then passes into nitrogen emptying air, pass into the concentration after vaporization is 1.5% hydrochloric acid vapour simultaneously, hydrochloric acid vapour passes into above reactor, and below out rear condensation is collected, and gas chromatographic detection furfural content is 14.31g/L, the output of furfural is 47.24g, and furaldehyde yield is 78.34%.
Embodiment 3:
Take 300g corn cob, take the FeCl of 15g
3be made into the aqueous solution of 200g, by biomass material and FeCl
3solution mixes, be placed in tubular reactor, tubular reactor adopts oil bath heating, controls tubular type temperature of reaction at 180 DEG C, then passes into nitrogen emptying air, pass into the concentration after vaporization is 3% hydrochloric acid vapour simultaneously, hydrochloric acid vapour passes into above reactor, and below out rear condensation is collected, and gas chromatographic detection furfural content is 14.3g/L, the output of furfural is 47.19g, and furaldehyde yield is 78.26%.
Comparison example 1, adopts Lewis acid separately
Take the corn cob of 300g, take the FeCl of 12g
3be made into the aqueous solution of 200g, by biomass material and FeCl
3solution mixes, be placed in tubular reactor, tubular reactor adopts oil bath heating, controls tubular type temperature of reaction at 180 DEG C, then passes into nitrogen emptying air, pass into water vapor simultaneously, water vapor passes into above reactor, and below out rear condensation is collected, and the content of gas chromatographic detection furfural is 8.74g/L, the amount calculating furfural is 28.83g, and furaldehyde yield is 47.82%.
Comparison example 2, adopts hydrochloric acid vapour separately
Take 300g corn cob and be placed in tubular reactor, tubular reactor adopts oil bath heating, control tubular type temperature of reaction at 180 DEG C, then pass into nitrogen emptying air, pass into the concentration after vaporization is 1.5% hydrochloric acid vapour simultaneously, and steam passes into above reactor, below out rear condensation is collected, the content of gas chromatographic detection furfural is 11.03g/L, and the amount calculating furfural is 36.39g, and furaldehyde yield is 60.34%.
Can obviously be found out by above data, the furaldehyde yield that the present invention adopts vapor phase acid and the common catalytic hydrolysis of Lewis acid to prepare furfural is greatly enhanced.
Claims (1)
1. a vapor phase acid and Lewis acid are total to the method that catalytic hydrolysis prepares furfural, it is characterized in that, by biomass material and Lewis acid aqueous solution even, be placed in the tubular reactor that temperature controls at 155-180 DEG C, pass into nitrogen purge, then pass into the hydrochloric acid vapour that concentration is 0.5-3% vaporization from one end of tubular reactor, collect phlegma from the other end of tubular reactor, phlegma is furfural crude product;
Lewis acidic consumption is the 1-5% of biomass material quality, and the mass concentration of the Lewis acid aqueous solution is 1.5-8%; Lewis acid is FeCl
3, AlCl
3, ZnCl
2or CuCl
2.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310576072.6A CN103554068B (en) | 2013-11-18 | 2013-11-18 | The method of furfural prepared by a kind of vapor phase acid and Lewis acid altogether catalytic hydrolysis |
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|---|---|---|---|
| CN201310576072.6A CN103554068B (en) | 2013-11-18 | 2013-11-18 | The method of furfural prepared by a kind of vapor phase acid and Lewis acid altogether catalytic hydrolysis |
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| Publication Number | Publication Date |
|---|---|
| CN103554068A CN103554068A (en) | 2014-02-05 |
| CN103554068B true CN103554068B (en) | 2015-12-09 |
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|---|---|---|---|
| CN201310576072.6A Expired - Fee Related CN103554068B (en) | 2013-11-18 | 2013-11-18 | The method of furfural prepared by a kind of vapor phase acid and Lewis acid altogether catalytic hydrolysis |
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| CN108727311A (en) * | 2018-05-14 | 2018-11-02 | 安徽理工大学 | A kind of furfural production new process of environmental protection |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201864677U (en) * | 2010-11-09 | 2011-06-15 | 河南省科学院能源研究所有限公司 | Device for coproduction of levulinate and furfural by biomass fractional hydrolysis |
| CN102260230A (en) * | 2011-05-17 | 2011-11-30 | 中国林业科学研究院林产化学工业研究所 | Method for preparing furfural by using two-step hydrolysis of biomass |
| CN102391218A (en) * | 2011-12-23 | 2012-03-28 | 吉林大学 | Method for preparing furfural by xylose dehydration through fixed bed catalysis |
| WO2012170520A1 (en) * | 2011-06-09 | 2012-12-13 | Micromidas Inc. | Utilizing a multiphase reactor for the conversion of biomass to produce substituted furans |
-
2013
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201864677U (en) * | 2010-11-09 | 2011-06-15 | 河南省科学院能源研究所有限公司 | Device for coproduction of levulinate and furfural by biomass fractional hydrolysis |
| CN102260230A (en) * | 2011-05-17 | 2011-11-30 | 中国林业科学研究院林产化学工业研究所 | Method for preparing furfural by using two-step hydrolysis of biomass |
| WO2012170520A1 (en) * | 2011-06-09 | 2012-12-13 | Micromidas Inc. | Utilizing a multiphase reactor for the conversion of biomass to produce substituted furans |
| CN102391218A (en) * | 2011-12-23 | 2012-03-28 | 吉林大学 | Method for preparing furfural by xylose dehydration through fixed bed catalysis |
Non-Patent Citations (2)
| Title |
|---|
| FeCl3 and acetic acid co-catalyzed hydrolysis of corncob for improving furfural production and lignin removal from residue;Liaoyuan Mao等;《Bioresource Technology》;20120725;第123卷;第324-331页 * |
| Seawater-based furfural production via corncob hydrolysis catalyzed by FeCl3 in acetic acid steam;Liaoyuan Mao等;《Green Chemistry》;20130109;第15卷(第3期);第731页表2、第735页图6、第736页左栏第2段 * |
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