CN110642813B - Preparation process of furfural - Google Patents

Preparation process of furfural Download PDF

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Publication number
CN110642813B
CN110642813B CN201910848616.7A CN201910848616A CN110642813B CN 110642813 B CN110642813 B CN 110642813B CN 201910848616 A CN201910848616 A CN 201910848616A CN 110642813 B CN110642813 B CN 110642813B
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Prior art keywords
furfural
aldehyde
pressure
wool
corncob
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CN110642813A (en
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冯维春
徐婷
王艳
王灏
梁辉
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CHEMICAL TECHNOLOGY ACADEMY OF SHANDONG PROVINCE
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CHEMICAL TECHNOLOGY ACADEMY OF SHANDONG PROVINCE
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a preparation process of furfural, which comprises the following steps: furfural is prepared by using a new catalyst to replace the traditional sulfuric acid catalysis and adopting a continuous refining method. The invention solves the problems of low product yield, high energy consumption in the production process, serious waste water and gas pollution and the like in the existing furfural preparation process. Provides a furfural preparation process with high efficiency, less pollution and low energy consumption.

Description

Preparation process of furfural
Technical Field
The invention relates to the field of chemical production, in particular to a preparation process of furfural.
Background
Furfural is also called as furaldehyde (alpha-furaldehyde) and has a molecular formula of C 5 H 4 O 2 The method comprises the steps of carrying out a first treatment on the surface of the English name: furfural. The furfural pure product is colorless liquid and has special fragrance like almond. The industrial product is brown liquid, and the color of the industrial product is changed into brown black quickly under the action of light, heat, air and inorganic acid. Melting point-38.7deg.C, boiling point 161.7 deg.C, relative density 1.1594 (20/4deg.C). Slightly soluble in cold water and soluble in hot water, ethanol, diethyl ether, benzene, acetone, etc. Is volatile and its vapor forms an explosive mixture with air. Furfural is an important organic chemical product, has active chemical properties, can prepare a plurality of derivatives through oxidation, condensation and other reactions, and can be used as a chemical product directly or indirectly derived from the raw material of the furfurol to 1600 or more, thereby being widely applied to the industries of medicines, pesticides, resins, daily chemicals, casting, textiles, petroleum and the like.
The existing preparation process of furfural comprises a one-step method and a two-step method, wherein hydrolysis of pentosan and dehydration cyclization of pentosan are respectively carried out in two different reactors. Since the optimal conditions for producing sugar by hydrolysis of pentosan and for producing furfural by dehydration of pentosan are different, the two reactions can be carried out separately, so that the utilization rate of raw materials and the yield of furfural can be remarkably improved. However, because the two-step method has high equipment investment, complex operation and immature second pentose dehydration process, the prior industrial production of furfural mainly adopts a one-step method, the one-step method has low equipment investment and simple operation, but the reaction temperature is high when preparing the furfural, so that the carbonization of sugar substances in plants can promote the side reaction of the furfural, the product yield is low (10-13 tons of corncobs are consumed for producing 1 ton of finished furfural product), the energy consumption is high in the production process (25 tons of steam are consumed for producing 1 ton of furfural, 150 tons of circulating cooling water) and the waste water and the waste gas pollution is serious (25 tons of waste water are produced for producing 1 ton of furfural). Therefore, the development of the furfural preparation process with high efficiency, less pollution and low energy consumption has very important significance.
Disclosure of Invention
Aiming at a series of problems existing in the existing furfural production process, the invention mainly solves the technical problem of providing a method for synthesizing furfural, which can improve the furfural production yield, reduce environmental pollution and reduce energy consumption.
In order to solve the technical problems, the technical scheme adopted by the application is as follows:
a preparation process of furfural comprises the following specific steps:
1) Adding corncob and a solid acid catalyst into a high-pressure reaction kettle, and controlling the temperature and the pressure to start the reaction, wherein the hairy aldehyde and water are evaporated out of the system;
2) Condensing the mixture of the wool aldehyde and water obtained in the step 1) by a condenser at the temperature of 10-25 ℃ and layering to separate the wool aldehyde at the lower layer;
3) Adding potassium bicarbonate into the wool aldehyde separated in the step 2) under stirring for alkali washing at 55 ℃ for 0.5h;
4) And (3) carrying out reduced pressure distillation on Mao Quan subjected to alkali washing in the step (3) at the temperature of 85-95 ℃ under the pressure of-0.09 MPa, and continuously refining to obtain a furfural product.
Preferably, the solid acid catalyst in the step 1) is a compound of aluminum phosphate and acetic acid or a compound of aluminum trichloride and acetic acid;
preferably, the mass ratio of the aluminum phosphate or the aluminum trichloride to the acetic acid in the step 1) is 4-6:1;
the mass ratio of the preferable catalyst to the corncob is 0.03-1.5:100;
preferably, the pressure in step 1) is 0.8MPa to 1MPa;
preferably, the temperature in step 1) is 105-115 ℃;
preferably, the particle size of the corncob in the step 1) is 0.5-1.5cm;
preferably, the ratio of potassium bicarbonate to hairy aldehyde is 0.11-0.15:1.
The beneficial effects of the invention are as follows: 1. sulfuric acid is adopted in the traditional one-step furfural processAs a catalyst, sulfuric acid is used for catalyzing excessive oxidation, carbonization and other side reactions, small molecular aldehyde and acid are easy to generate, the reaction yield is low, the environment pollution is serious when aldehyde slag containing sulfuric acid is combusted, and each 1 ton of furfural is produced to produce SO 2 The exhaust gas is about 36m 3 . As the acyl in the corncob fiber molecules is broken to generate acetic acid, aluminum phosphate and acetic acid or aluminum trichloride and acetic acid are compounded to be used as a catalyst, the catalytic effect is enhanced, the furfural yield is improved, the corrosion to equipment is small, no sulfuration gas and high-concentration acid-containing wastewater are generated, and the problem of environmental pollution caused by wastewater is solved. 2. The aldehyde slag is applied to cogeneration, solves the problem of environmental pollution caused by the combustion and emission of the traditional process of sulfur-containing aldehyde slag, and accords with the related policies of national biomass energy development planning energy utilization and industry upgrading. 3. The refining of the furfural adopts a continuous distillation mode, and compared with the traditional process, the energy consumption is reduced.
Detailed Description
Example 1
A preparation process of furfural comprises the following specific steps:
1) Adding corncob and a solid acid catalyst into a high-pressure reaction kettle, and controlling the temperature and the pressure to start the reaction, wherein the hairy aldehyde and water are evaporated out of the system;
2) Condensing the furfural and water obtained in the step 1) by a condenser at 10 ℃ and layering to separate lower layer wool aldehyde.
3) Adding potassium bicarbonate into the wool aldehyde separated in the step 2) under stirring, and performing alkali washing for 0.5h at 55 ℃.
4) And (3) carrying out reduced pressure distillation and continuous refining on Mao Quan subjected to alkali washing in the step (3) at the temperature of 95 ℃ under the pressure of-0.09 MPa to obtain a furfural product. The yield thereof was found to be 95.5%.
Preferably, the solid acid catalyst in the step 1) is a compound of aluminum phosphate and acetic acid or a compound of aluminum trichloride and acetic acid;
preferably, the mass ratio of the aluminum phosphate or the aluminum trichloride to the acetic acid in the step 1) is 4:1;
preferably, the mass ratio of the catalyst to the corncob is 0.03:100;
preferably, the pressure in step 1) is 1MPa;
preferably, the temperature described in step 1) is 110 ℃.
Preferably, the particle size of the corncob in step 1) is 0.5cm;
preferably, the ratio of potassium bicarbonate to hairy aldehyde is 0.11:1.
Example 2
A preparation process of furfural comprises the following specific steps:
1) Adding corncob and a solid acid catalyst into a high-pressure reaction kettle, and controlling the temperature and the pressure to start the reaction, wherein the hairy aldehyde and water are evaporated out of the system;
2) Condensing the furfural and water obtained in the step 1) by a condenser at 10 ℃ and layering to separate lower layer wool aldehyde.
3) Adding potassium bicarbonate into the wool aldehyde separated in the step 2) under stirring, and performing alkali washing for 0.5h at 55 ℃.
4) And (3) carrying out reduced pressure distillation at the temperature of 85 ℃ under the pressure of-0.09 MPa on Mao Quan subjected to alkali washing in the step (3), and continuously refining to obtain a furfural product with the yield of 95%.
Preferably, the solid acid catalyst in the step 1) is a compound of aluminum phosphate and acetic acid or a compound of aluminum trichloride and acetic acid;
preferably, the mass ratio of the aluminum phosphate or the aluminum trichloride to the acetic acid in the step 1) is 6:1;
preferably, the mass ratio of the catalyst to the corncob is 0.03:100;
preferably, the pressure in step 1) is 0.8MPa;
preferably, the temperature described in step 1) is 105 ℃.
Preferably, the particle size of the corncob in step 1) is 1.5cm;
preferably, the ratio of potassium bicarbonate to hairy aldehyde is 0.15:1.
Example 3
A preparation process of furfural comprises the following specific steps:
1) Adding corncob and a solid acid catalyst into a high-pressure reaction kettle, and controlling the temperature and the pressure to start the reaction, wherein the hairy aldehyde and water are evaporated out of the system;
2) Condensing the furfural and water obtained in the step 1) by a condenser at 25 ℃ and layering to separate lower layer wool aldehyde.
3) Adding potassium bicarbonate into the wool aldehyde separated in the step 2) under stirring, and performing alkali washing for 0.5h at 55 ℃.
4) And (3) carrying out reduced pressure distillation at the temperature of 95 ℃ under the pressure of-0.09 MPa on Mao Quan subjected to alkali washing in the step (3), and continuously refining to obtain a furfural product with the yield of 95.2%.
Preferably, the solid acid catalyst in the step 1) is a compound of aluminum phosphate and acetic acid or a compound of aluminum trichloride and acetic acid;
preferably, the mass ratio of the aluminum phosphate or the aluminum trichloride to the acetic acid in the step 1) is 5:1;
preferably, the mass ratio of the catalyst to the corncob is 1.5:100;
preferably, the pressure in step 1) is 1MPa;
preferably, the temperature described in step 1) is 115 ℃.
Preferably, the particle size of the corncob in step 1) is 1cm;
preferably, the ratio of potassium bicarbonate to hairy aldehyde is 0.11:1.
Example 4
A preparation process of furfural comprises the following specific steps:
1) Adding corncob and a solid acid catalyst into a high-pressure reaction kettle, and controlling the temperature and the pressure to start the reaction, wherein the hairy aldehyde and water are evaporated out of the system;
2) Condensing the furfural and water obtained in the step 1) by a condenser at 20 ℃ and layering to separate lower layer wool aldehyde.
3) Adding potassium bicarbonate into the wool aldehyde separated in the step 2) under stirring, and performing alkali washing for 0.5h at 55 ℃.
4) And (3) performing reduced pressure distillation on Mao Quan subjected to alkali washing in the step (3) at the pressure of minus 0.09MPa and the temperature of 90 ℃ to obtain a furfural product through continuous refining. The yield thereof was found to be 95%.
Preferably, the solid acid catalyst in the step 1) is a compound of aluminum phosphate and acetic acid or a compound of aluminum trichloride and acetic acid;
preferably, the mass ratio of the aluminum phosphate or the aluminum trichloride to the acetic acid in the step 1) is 4:1;
preferably, the mass ratio of the catalyst to the corncob is 0.1:100;
preferably, the pressure in step 1) is 1MPa;
preferably, the temperature described in step 1) is 110 ℃.
Preferably, the particle size of the corncob in step 1) is 1.5cm;
preferably, the ratio of potassium bicarbonate to hairy aldehyde is 0.12:1.
While the foregoing describes the embodiments of the present invention, it is not intended to limit the scope of the present invention, and various modifications or variations may be made by those skilled in the art without the need for inventive effort on the basis of the technical solutions of the present invention.

Claims (6)

1. The preparation process of the furfural is characterized by comprising the following specific steps of:
1) Adding corncob and a solid acid catalyst into a high-pressure reaction kettle, and controlling the temperature to be 105-115 ℃ and the pressure to start the reaction, wherein the wool aldehyde and water are evaporated from the system;
2) Condensing the mixture of the wool aldehyde and water obtained in the step 1) by a condenser at the temperature of 10-25 ℃ and layering to separate the wool aldehyde at the lower layer;
3) Adding potassium bicarbonate into the wool aldehyde separated in the step 2) under stirring for alkali washing at 55 ℃ for 0.5h;
4) Performing reduced pressure distillation at a temperature of 85-95 ℃ under a pressure of-0.09 MPa on Mao Quan subjected to alkali washing in the step 3), and continuously refining to obtain a furfural product;
the solid acid catalyst in the step 1) is a compound of aluminum phosphate and acetic acid or a compound of aluminum trichloride and acetic acid.
2. The process for preparing furfural according to claim 1, wherein the mass ratio of aluminum phosphate or aluminum trichloride to acetic acid in step 1) is 4-6:1.
3. The process for preparing furfural according to claim 1, wherein the mass ratio of the solid acid catalyst to the corncob in step 1) is 0.03-1.5:100.
4. The process for preparing furfural according to claim 1, wherein the pressure in step 1) is 0.8MPa to 1MPa.
5. The process for preparing furfural according to claim 1, wherein the particle size of the corncob in step 1) is 0.5-1.5 cm.
6. The process for preparing furfural according to claim 1, wherein step 3) is 0.11-0.15:1 of potassium bicarbonate to mucosals.
CN201910848616.7A 2019-09-09 2019-09-09 Preparation process of furfural Active CN110642813B (en)

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Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101486695B (en) * 2009-02-10 2011-08-17 清华大学 Solid acid catalysis and supercritical extraction coupled furfural preparation method and apparatus
CN102336728A (en) * 2011-10-28 2012-02-01 南京林业大学 Method for preparing furfural from fiber pentosan hydrolysate by using composite solid acid as catalyst
CN205420242U (en) * 2015-10-23 2016-08-03 上海毅知实业有限公司 Furfural cleaner production assembly line
CN105198842A (en) * 2015-10-23 2015-12-30 上海毅知实业有限公司 Clean production line for furfural and production method of furfural
CN109776460A (en) * 2019-03-27 2019-05-21 北京林业大学 A method of Furfural Production from Xylose is catalyzed using solid acid catalyst
CN109970690B (en) * 2019-04-23 2021-02-12 北京林业大学 Method for green and efficient preparation of furfural by catalyzing biomass with solid acid

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