CN103554068A - Method for preparing furaldehyde through co-catalysis hydrolysis by gas phase acid and Lewis acid - Google Patents
Method for preparing furaldehyde through co-catalysis hydrolysis by gas phase acid and Lewis acid Download PDFInfo
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- CN103554068A CN103554068A CN201310576072.6A CN201310576072A CN103554068A CN 103554068 A CN103554068 A CN 103554068A CN 201310576072 A CN201310576072 A CN 201310576072A CN 103554068 A CN103554068 A CN 103554068A
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- Prior art keywords
- acid
- furfural
- lewis acid
- tubular reactor
- furaldehyde
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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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- Chemical & Material Sciences (AREA)
- 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 the technical field of preparation of furaldehyde, and in particular relates to a method for preparing furaldehyde through co-catalysis hydrolysis by gas phase acid and Lewis acid. The method comprises the steps of uniformly mixing a biomass raw material with a Lewis acid aqueous solution, putting the mixture into a tubular reactor, introducing nitrogen to empty air, then introducing vaporized hydrochloric acid vapor from one end of the tubular reactor, and collecting condensate from the other end of the tubular reactor, wherein the condensate is a furaldehyde crude product. According to the method disclosed by the invention, the Lewis acid co-catalyst is added, so that the yield of furaldehyde is improved, the corrosion to equipment is avoided at the same time, the discharge of any acid waste liquid is avoided, and environmental pollutions are avoided.
Description
technical field
The invention belongs to furfural preparing technical field, be specifically related to a kind of vapor phase acid and Lewis acid of adopting and be total to the method that catalytic hydrolysis is prepared furfural.
background technology
Furfural is by piperylene, under sour effect, to be hydrolyzed to generate pentose, then is formed by pentose cyclodehydration.In the production process of furfural, can take the operations such as stripping, solvent extraction that the furfural of generation is shifted out in time from system.In the last few years, people developed supercritical CO
2deng extraction, shift out the novel method of furfural.The method of producing in the world furfural at present has sulfuric acid process, method of acetic acid, salt acid system, inorganic salt method.China furfural production factory more than 95% adopts sulfuric acid catalysis Fa， minority producer to use salt acid system.Sulfuric acid process is classical furfural production method, with 3% ~ 6% dilute sulphuric acid, makes catalyzer, and raw material and catalyzer are depressed to boiling adding, with high pressure or superheated vapour, take reactant out of, 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.Method of acetic acid is catalyzer with the byproduct acetic acid in furfural production process, under High Temperature High Pressure, produces furfural, 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.Salt acid system is under normal pressure, to use hydrochloric acid to prepare the method for furfural for catalyzer hydrolysis, and raw material availability is high, and product yield is high, and quality is good, but technical process is long, operation control system complexity, and investment of production is large, and corrodibility is comparatively serious.Inorganic salt method is mainly to take superphosphate to prepare the method for furfural as catalyzer hydrolysis, 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 of 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 object of the present invention is to provide employing vapor phase acid and the Lewis acid that a kind of yield is higher to be total to the method that catalytic hydrolysis is prepared furfural.
The present invention is by the following technical solutions:
A kind of vapor phase acid and Lewis acid are total to the method that catalytic hydrolysis is prepared furfural, biomass material and Lewis acid aqueous solution is even, be placed in tubular reactor, pass into nitrogen purge, then from one end of tubular reactor, pass into the hydrochloric acid vapour of vaporization, from the other end of tubular reactor, collect phlegma, phlegma is furfural crude product.
The temperature of described tubular reactor is controlled at 155-180 ℃.
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 compares with existing furfural production technology, and its feature, advantage and positively effect are mainly reflected in the following aspects:
The one, reaction is carried out under normal pressure, and temperature of reaction is more than the dew point of hydrochloric acid, has avoided the corrosion to equipment, adds Lewis acid promotor, has improved furaldehyde yield;
The 2nd, vapor phase acid (hydrochloric acid vapour) catalyzer that reaction adopts can reclaim and recycle completely, without any acid waste liquid discharge, has avoided 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 ℃, then passes into nitrogen emptying air, the concentration simultaneously passing into after vaporization is 1% hydrochloric acid vapour, hydrochloric acid vapour passes into from reactor top, and collect below out rear condensation, 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 ℃, then passes into nitrogen emptying air, the concentration simultaneously passing into after vaporization is 1.5% hydrochloric acid vapour, hydrochloric acid vapour passes into from reactor top, and collect below out rear condensation, 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 ℃, then passes into nitrogen emptying air, the concentration simultaneously passing into after vaporization is 3% hydrochloric acid vapour, hydrochloric acid vapour passes into from reactor top, and collect below out rear condensation, 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 separately Lewis acid
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 ℃, then passes into nitrogen emptying air, pass into water vapor simultaneously, water vapor passes into from reactor top, and collect below out rear condensation, and the content of gas chromatographic detection furfural is 8.74g/L, the amount of calculating furfural is 28.83g, and furaldehyde yield is 47.82%.
Comparison example 2, adopts separately hydrochloric acid vapour
Take 300g corn cob and be placed in tubular reactor, tubular reactor adopts oil bath heating, control tubular type temperature of reaction at 180 ℃, then pass into nitrogen emptying air, the concentration simultaneously passing into after vaporization is 1.5% hydrochloric acid vapour, and steam passes into from reactor top, collect below out rear condensation, the content of gas chromatographic detection furfural is 11.03g/L, and the amount of calculating furfural is 36.39g, and furaldehyde yield is 60.34%.
By above data, can obviously be found out, 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 (5)
- A vapor phase acid and Lewis acid altogether catalytic hydrolysis prepare the method for furfural, it is characterized in that, biomass material and Lewis acid aqueous solution is even, be placed in tubular reactor, pass into nitrogen purge, then from one end of tubular reactor, pass into the hydrochloric acid vapour of vaporization, from the other end of tubular reactor, collect phlegma, phlegma is furfural crude product.
- 2. vapor phase acid as claimed in claim 1 and Lewis acid are total to the method that catalytic hydrolysis is prepared furfural, it is characterized in that, the temperature of described tubular reactor is controlled at 155-180 ℃.
- 3. vapor phase acid as claimed in claim 1 or 2 and Lewis acid are total to the method that catalytic hydrolysis is prepared furfural, it is characterized in that, 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%.
- 4. vapor phase acid as claimed in claim 3 and Lewis acid are total to the method that catalytic hydrolysis is prepared furfural, it is characterized in that, Lewis acid is FeCl 3, AlCl 3, ZnCl 2or CuCl 2.
- 5. vapor phase acid as claimed in claim 1 and Lewis acid are total to the method that catalytic hydrolysis is prepared furfural, it is characterized in that, the concentration of hydrochloric acid vapour is 0.5-3%.
Priority Applications (1)
| 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 |
Applications Claiming Priority (1)
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103554068A true CN103554068A (en) | 2014-02-05 |
| CN103554068B 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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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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
- 2013-11-18 CN CN201310576072.6A patent/CN103554068B/en not_active Expired - Fee Related
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 |
|---|
| LIAOYUAN MAO等: "FeCl3 and acetic acid co-catalyzed hydrolysis of corncob for improving furfural production and lignin removal from residue", 《BIORESOURCE TECHNOLOGY》 * |
| LIAOYUAN MAO等: "Seawater-based furfural production via corncob hydrolysis catalyzed by FeCl3 in acetic acid steam", 《GREEN CHEMISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727311A (en) * | 2018-05-14 | 2018-11-02 | 安徽理工大学 | A kind of furfural production new process of environmental protection |
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| CN103554068B (en) | 2015-12-09 |
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Granted publication date: 20151209 Termination date: 20191118 |