CN109628128B - CO (carbon monoxide)2Method for preparing furfural by hydrothermal liquefaction of agricultural and forestry waste under atmosphere - Google Patents

CO (carbon monoxide)2Method for preparing furfural by hydrothermal liquefaction of agricultural and forestry waste under atmosphere Download PDF

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CN109628128B
CN109628128B CN201811594824.0A CN201811594824A CN109628128B CN 109628128 B CN109628128 B CN 109628128B CN 201811594824 A CN201811594824 A CN 201811594824A CN 109628128 B CN109628128 B CN 109628128B
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agricultural
furfural
reaction kettle
forestry
reaction
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CN109628128A (en
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王贤华
曲磊
陈应泉
杨海平
杨晴
曾阔
陈伟
张世红
陈汉平
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Huazhong University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/14—Production of inert gas mixtures; Use of inert gases in general
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/086—Characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin

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  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses CO2The preparation method of the furfural by hydrothermal liquefaction of agricultural and forestry waste under the atmosphere comprises the following steps: s1: collecting agricultural and forestry wastes, crushing and screening the agricultural and forestry wastes, adding the agricultural and forestry wastes into a hydrothermal reaction kettle, and mixing the agricultural and forestry wastes with deionized water to form a mixed solution with the mass-volume ratio of 1:15 to 1: 5;s2: with CO2Purging the kettle body, discharging air in the reaction kettle, closing the air outlet valve, and filling 0-2 Mpa CO2Sealing the reaction kettle, heating the reaction kettle to 150-250 ℃ under stirring, and keeping the temperature for 10-50 minutes; s3: cooling the hydrothermal reaction kettle to room temperature, decompressing, collecting gas, collecting a solid-liquid mixture after reaction in the reaction kettle, and performing vacuum filtration separation to obtain a solid part and a liquid part; s4: and (3) extracting and extracting the liquid part by using an organic solvent, separating and filtering an organic phase, removing the organic solvent, and obtaining the furfural-rich bio-oil by rotary evaporation. By using CO2And (3) making an inert atmosphere, and selecting proper parameters to jointly improve the selectivity and the yield of the furfural.

Description

CO (carbon monoxide)2Method for preparing furfural by hydrothermal liquefaction of agricultural and forestry waste under atmosphere
Technical Field
The invention belongs to the technical field of biomass energy, and particularly relates to CO2A method for preparing furfural by hydro-thermal liquefaction of agricultural and forestry waste under atmosphere.
Background
Furfural, also known as 2-furaldehyde, is a natural precursor of a series of furyl chemicals and solvents, has very high application value, and is widely applied to organic synthesis, analytical reagents, raw material preparation of medicines and industrial products, and the like. At present, furfural preparation methods mainly comprise hydrolysis liquefaction, catalysis, pyrolysis of biomass and the like. The biomass is rich in hemicellulose, and the hemicellulose is further degraded into furfural. In the hydrolysis method, hemicellulose is hydrolyzed under the action of acid and water to generate xylose, and the xylose is subjected to isomerization and continuous dehydration reaction to generate furfural. Pyrolysis of biomass refers to the process of opening the bonds of cellulose and hemicellulose to form small molecular substances under certain high temperature conditions. The yield of the furfural can be increased by selecting a catalyst and controlling the temperature, and in industry, the furfural is obtained by heating a digester by steam and extracting the furfural from hemicellulose in the lignocellulose biomass under the catalysis of dilute sulfuric acid.
However, the existing preparation method has certain disadvantages:
1. n is commonly used in the prior art2As an inert gas for the reaction, the yield of furfural is generally to be further improved;
2. patent application No. 201610692355.0 discloses a method for preparing furfural from oil tea shells, which mentions carbon dioxide as a weakly acidic gas catalyst, but uses a catalyst promoter in combination. The existing catalytic system has more side reactions, which can reduce the selectivity of pentose to furfural and lead to larger furfural loss;
3. in the prior art, 25-35 t of water vapor is consumed for preparing each ton of furfural, the reaction time is long, and the energy consumption is huge and the cost is high by using the steam as a heat source and an extracting agent; and the problems of high energy consumption and high catalyst cost in the pyrolysis process are to be improved.
4. The diluted acid is used as a catalyst for corrosion-prone equipment, expensive metal equipment is consumed, and the maintenance cost and the environmental pollution are serious. And the separation and the recycling of the acid furfural are very difficult, while the dilute acid hydrolysis method can also cause a large amount of acid furfural wastewater, so the treatment difficulty is very high.
In a word, the furfural industry is a typical industry with high energy consumption and heavy pollution, and reports that the furfural preparation method has great effects on improving the yield, reducing the energy consumption, reducing the waste water discharge and slowing down the equipment corrosion, but still can not completely solve the pollution problem or can not be applied due to high cost.
Disclosure of Invention
In response to the above-identified deficiencies in the art or needs for improvement, the present inventionClearly provide a CO2The preparation method of furfural by hydrothermal liquefaction of agricultural and forestry waste under atmosphere comprises mixing agricultural and forestry waste with deionized water, and adding CO2Reacting in a reaction kettle at constant temperature under the atmosphere, and finally extracting and separating the reaction mixture to obtain the biological oil rich in furfural. The invention adopts CO2An inert atmosphere is used to replace a dilute sulfuric acid catalyst, and proper parameters are selected to improve the selectivity and the yield of the furfural.
In order to achieve the above object, the present invention provides a CO2The preparation method of the furfural by hydrothermal liquefaction of agricultural and forestry waste under the atmosphere comprises the following steps:
s1: collecting agricultural and forestry wastes, crushing and screening the agricultural and forestry wastes, adding the agricultural and forestry wastes into a hydrothermal reaction kettle, and mixing the agricultural and forestry wastes with deionized water to form mixed liquid;
s2: with CO2Purging the kettle body, exhausting air in the reaction kettle, then closing the air outlet valve, and filling CO2Then sealing the reaction kettle, heating the reaction kettle to 150-250 ℃ under stirring, and keeping the temperature for 10-50 minutes;
s3: cooling the hydrothermal reaction kettle to room temperature, decompressing and collecting gas, collecting a solid-liquid mixture after reaction in the reaction kettle, and performing vacuum filtration and separation on the solid-liquid mixture to obtain a solid part and a liquid part;
s4: and (3) extracting and extracting the liquid part obtained in the S3 by using an organic solvent, separating and filtering an organic phase, removing the organic solvent, and obtaining the biological oil rich in the furfural by rotary evaporation.
Further, in step S2, the CO2The pressure of the pressure is 0MPa to 2 MPa.
Further, in step S1, the grain size of the agricultural and forestry waste is in the range of 60 to 120 meshes.
Further, in step S1, the agricultural and forestry waste includes one or more of rice hulls, straws, corn cobs or bamboo shavings.
Further, in step S1, the mass-to-volume ratio of the mixed solution is 1:5 to 1: 15.
Further, the organic solvent comprises one or more of diethyl ether, dichloromethane or ethyl acetate.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) CO of the invention2The preparation method of furfural by hydrothermal liquefaction of agricultural and forestry waste under atmosphere comprises mixing agricultural and forestry waste with deionized water, and adding CO2Reacting in a reaction kettle at constant temperature under the atmosphere, and finally extracting and separating the reaction mixture to obtain the biological oil rich in furfural. The invention adopts CO2An inert atmosphere is used to replace a dilute sulfuric acid catalyst, and proper parameters are selected to improve the selectivity and the yield of the furfural.
(2) CO of the invention2Method for preparing furfural by hydrothermal liquefaction of agricultural and forestry waste under atmosphere, CO2Dissolving in water at high temperature and high pressure to form weak acid, CO2The weak acid environment brought by the atmosphere inhibits the generation of by-products acetic acid and other oxygen-containing substances, the obtained bio-oil has high furfural content and few by-products, the stability and the quality of the bio-oil are improved, and good conditions are provided for further purification in the later period.
(3) CO of the invention2Compared with N, the preparation method of furfural by hydrothermal liquefaction of agricultural and forestry waste under atmosphere2，CO2The catalyst can not only exhaust air, but also be dissolved in water to form carbonic acid to participate in system reaction, can be ionized to generate a large amount of hydrogen ions under the conditions of high temperature and high pressure, reduces the pH value of a reaction medium, plays a certain role in acid catalysis, replaces a dilute sulfuric acid catalyst in the traditional preparation process, and is beneficial to relieving the corrosion problem caused by dilute sulfuric acid in the traditional preparation method.
(4) CO of the invention2The invention discloses a method for preparing furfural by hydrothermal liquefaction of agricultural and forestry waste under atmosphere, which adopts CO2Making an inert atmosphere and reasonably utilizing CO2The method is favorable for reducing the emission of greenhouse gases, has low reaction temperature and achieves the aims of energy conservation and emission reduction on the whole.
(5) CO of the invention2A method for preparing furfural by hydrothermal liquefaction of agricultural and forestry wastes under an atmosphere utilizes the agricultural and forestry wastes to prepare furfural with high added value in a hydrothermal mode, and raw materials are prepared without dryingThe process does not need to add any catalyst, so that the energy consumption is reduced, the operation complexity is reduced, meanwhile, the organic solvent for extraction in the reaction process can be recycled, the cost is reduced, and the green preparation of furfural and the high-value utilization of biomass waste are realized.
Drawings
FIG. 1 shows a CO according to an embodiment of the present invention2A process flow chart of a preparation method of furfural by hydrothermal liquefaction of agricultural and forestry waste under atmosphere;
FIG. 2 shows rice hull CO according to an embodiment of the present invention2A GC-MS spectrogram of component analysis of a liquid product prepared by hydrothermal liquefaction in an atmosphere;
FIG. 3 shows two corn stalks CO according to an embodiment of the present invention2A GC-MS spectrogram of component analysis of a liquid product prepared by hydrothermal liquefaction in an atmosphere;
FIG. 4 shows three peanut shells CO according to an embodiment of the present invention2A GC-MS spectrogram of component analysis of a liquid product prepared by hydrothermal liquefaction in an atmosphere;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Fig. 1 is a process flow diagram related to a method for preparing furfural by hydrothermal liquefaction of agricultural and forestry waste under a CO2 atmosphere, and as shown in fig. 1, the method for preparing furfural by hydrothermal liquefaction of agricultural and forestry waste under a CO2 atmosphere according to the embodiment of the present invention includes the following steps:
s1: collecting agricultural and forestry wastes, crushing and screening the agricultural and forestry wastes until the particle size is 60-120 meshes, adding the agricultural and forestry wastes into a hydrothermal reaction kettle, and mixing the agricultural and forestry wastes with deionized water to form a mixed solution with the mass-volume ratio of 1:5 to 1: 15;
s2: purging the kettle body with CO2 to exhaust air in the reaction kettle, then closing the air outlet valve, filling 0 Mpa-2 Mpa CO2, and then sealing the reaction kettle to heat the reaction kettle to 150-250 ℃ under stirring and keep the temperature for 10-50 minutes;
s3: cooling the hydrothermal reaction kettle to room temperature, decompressing, collecting gas, collecting a solid-liquid mixture after reaction in the reaction kettle, and performing vacuum filtration and separation on the solid-liquid mixture to obtain a solid part and a liquid part;
s4: and (4) extracting the liquid part obtained by separation in the S3 with an organic solvent, separating and filtering the organic phase, removing the organic solvent, and performing rotary evaporation to obtain the biological oil rich in furfural.
Specifically, in S1, after the agricultural and forestry waste is crushed, the mass volume ratio of the crushed agricultural and forestry waste mixed with deionized water is selected from 1:5 to 1:15, when the mass-to-volume ratio is more than 1:15, selecting an excessively high mass-to-volume ratio, wherein when the crushed agricultural and forestry waste is combined with deionized water, the effective components are excessively diluted due to excessive solvent, and finally, the reaction activity is reduced when the crushed agricultural and forestry waste is reacted in a reaction kettle; in addition, if the mass-to-volume ratio is too small, the crushed agricultural and forestry waste cannot be sufficiently contacted with deionized water, so that the subsequent reaction cannot be sufficiently carried out in a reaction kettle, the activity is reduced, and the yield is influenced. Further, in step S2, CO2The initial pressure for filling is 0 Mpa-2 Mpa, if the initial pressure is too low, air can not be exhausted, air is doped in the reaction process, and the whole reaction is influenced or a supercritical environment can not be formed. The over-high initial pressure of the filling can lead to the over-high whole reaction pressure, and the long-term use is easy to cause the abrasion of the equipment, which is not beneficial to the long-term maintenance and use of the equipment. CO22The water-soluble carbonic acid can be formed to participate in the system reaction, and the air is isolated, so that the pH value of the reaction medium is reduced, and a certain acid catalysis effect is achieved. Mixing agricultural and forestry wastes with deionized water and then adding CO in a reaction kettle2The reaction temperature under the atmosphere is selected to be 150-250 ℃, the proper temperature rise is favorable for accelerating the movement rate of the reaction, but when the reaction temperature exceeds 250 ℃, the reaction rate of furfural decomposition is accelerated due to overhigh temperature, and the polymerization reaction among furfural molecules is accelerated due to overhigh temperature, so that the yield of furfural is reduced; conversely, too low a temperature is not favorable for the reaction to take place sufficiently. In addition, the reaction time in the reaction kettle is setThe reaction time is 10-50 minutes, the yield of the furfural is continuously increased along with the increase of the reaction time, but the reaction time is too long, the decomposition rate of the furfural is greater than the generation rate of the furfural, the final yield of the furfural is reduced, and the reaction time is too long, so that the reaction economy is not facilitated; the reaction time is less than 10 minutes, and the reaction time is too short, so that the reaction is not fully performed, and the yield of the furfural is reduced.
Further, according to the method for preparing the furfural by hydrothermal liquefaction of the agricultural and forestry waste under the CO2 atmosphere, the mass-volume ratio of the agricultural and forestry waste to the deionized water is selected from the following steps: 15 to 1: 5; selecting the initial pressure of CO2 to be 0-2 Mpa; selecting the raw materials to react in a reaction kettle at the temperature of between 150 and 250 ℃; and the reaction time is selected to be 10-50 minutes; the invention combines CO in the reaction system under the combined action of proper mass-volume ratio of raw materials to solvent, reaction temperature and reaction time2Dissolving in water at high temperature and high pressure to form weak acid, CO2Dissolving in water at high temperature and high pressure to form weak acid, CO2The weak acid environment brought by the atmosphere inhibits the generation of acetic acid and other oxygen-containing substances, so that the prepared furfural has high relative content and few byproducts.
Further, according to the preparation method of the furfural by hydrothermal liquefaction of the agricultural and forestry waste under the CO2 atmosphere, the furfural with a high added value is prepared by using the agricultural and forestry waste in a hydrothermal manner, in the step S1, the raw material is directly mixed with deionized water without pretreatment steps such as drying, any catalyst is not required to be added in the preparation process, the energy consumption is reduced, the operation complexity is reduced, meanwhile, the organic solvent for extraction in the reaction process can be recycled, the cost is reduced, and the green preparation of the furfural and the high-value utilization of the biomass waste are realized.
Example 1:
CO (carbon monoxide)2The preparation method of the furfural by hydrothermal liquefaction of agricultural and forestry waste under the atmosphere comprises the following steps:
s1: weighing 10g of rice hull, placing the rice hull into a 500ml high-temperature high-pressure hydrothermal reaction kettle, and adding 100ml of deionized water;
s2: sealing the reaction kettle, exhausting air in the reaction kettle, and charging CO with initial pressure of 2Mpa2Turning on a heating switch, setting the stirring speed to be 200r/min, raising the temperature to 200 ℃ at the speed of 8 ℃/min, keeping the temperature for 30min, and immediately turning off the heating switch;
s3: after the reaction kettle is cooled to room temperature, collecting generated gas, opening the reaction kettle, taking out a reaction mixture, and utilizing CH2Cl2Cleaning the inner wall of the reaction kettle and the stirrer;
s4: by CH2Cl2Extraction of the reaction mixture, CH2Cl2Extracting with the reaction mixture at a ratio of 1:2 for 30min, separating the extractive solution, and filtering CH with vacuum filtration device2Cl2Phase, recovering CH by reduced pressure distillation2Cl2And obtaining the biological oil rich in furfural.
Further, as shown in fig. 2, the relative content of high value-added furfural in the liquid product is as high as 94.6%, the main components in the bio-oil are furfural, vanillin and the like, the content of acetic acid and other oxygen-containing substances in the bio-oil is reduced, the selectivity of furfural in the bio-oil is improved, and thus the quality of the bio-oil is improved; under the same conditions, the atmosphere is changed to N2Then, the relative distribution content of furfural in the hydrothermal solution is only 58.4%, and the hydrothermal solution contains a large amount of other phenols, aldehydes and ketones. Indicating CO2The atmosphere is beneficial to improving the selectivity and the yield of the furfural and realizing CO2And (4) emission reduction.
Example 2:
s1: weighing 10g of cornstalks, putting the cornstalks into a 500ml high-temperature high-pressure hydrothermal reaction kettle, and adding 150ml of deionized water;
s2: sealing the reaction kettle, exhausting air in the reaction kettle, filling CO2 with the initial pressure of 1.5Mpa, opening a heating switch, setting the stirring speed to be 200r/min, heating to 200 ℃ at the speed of about 8 ℃/min, keeping the temperature for 30min, and immediately closing the heating switch;
s3: after the reaction kettle is cooled to room temperature, collecting generated gas, opening the reaction kettle, taking out a reaction mixture, and cleaning the inner wall of the reaction kettle and a stirrer by using ether;
s4: and (3) extracting the mixture by using diethyl ether, wherein the ratio of the diethyl ether to the reaction mixture is 1:2, the extraction time is 12 hours, filtering the diethyl ether phase by using a vacuum filtration device, and recovering the diethyl ether by reduced pressure distillation to obtain the biological oil rich in furfural.
Further, as shown in FIG. 3, the components were measured by GC-MS. The main components are shown in figure 3, the relative content of the high-value-added furfural in the liquid product is up to 88.32%, and the relative content of the furfural with other small amount of aldehydes and phenolic substances is improved by 29.92% compared with the nitrogen atmosphere. The high furfural content demonstrates the feasibility and stability of the process.
Example 3:
s1: weighing 10g of peanut shells, placing the peanut shells in a 500ml high-temperature high-pressure hydrothermal reaction kettle, and adding 50ml of deionized water;
s2: sealing the reaction kettle, exhausting air in the reaction kettle, filling CO2 with the initial pressure of 1Mpa, opening a heating switch, setting the stirring speed at 200r/min, heating to 200 ℃ at the speed of about 8 ℃/min, keeping the temperature for 30min, and immediately closing the heating switch;
s3: after the reaction kettle is cooled to room temperature, collecting generated gas, opening the reaction kettle, taking out a reaction mixture, and cleaning the inner wall of the reaction kettle and a stirrer by using ether;
s4: and (3) extracting the mixture by using diethyl ether, wherein the ratio of the diethyl ether to the reaction mixture is 1:2, the extraction time is 12 hours, filtering the diethyl ether phase by using a vacuum filtration device, and recovering the diethyl ether by reduced pressure distillation to obtain the biological oil rich in furfural.
Further, as shown in FIG. 4, the components were measured by GC-MS. The main components are shown in figure 4, the relative content of high-value-added furfural in the liquid product is as high as 86.40%, the relative content is improved by 28% under the atmosphere of nitrogen, and other small amounts of aldehydes and phenolic substances are accompanied. The high furfural content further demonstrates the feasibility and stability of the process.
Further, with reference to fig. 2 to 4, the method for preparing furfural by hydrothermal liquefaction of agricultural and forestry waste under the atmosphere of CO2 according to the present invention can prepare furfural with a relatively high content for various biomass raw materials, and the method for preparing furfural according to the present invention has a wide application range; compared with the commonly used nitrogen atmosphere in the prior art, the method for preparing furfural has few byproducts, improves the stability and the quality of the biological oil, and provides good conditions for further purification in the later period.
CO of the invention2The preparation method of furfural by hydrothermal liquefaction of agricultural and forestry wastes under atmosphere comprises mixing agricultural and forestry wastes with water, and adding CO2Reacting in a reaction kettle at constant temperature under the atmosphere, and finally extracting and separating the reaction mixture to obtain the biological oil rich in furfural. The invention adopts CO2The catalyst is used as inert atmosphere to replace dilute sulfuric acid catalyst, so that the selectivity and yield of furfural are improved. And reasonably utilizes CO2The method is favorable for reducing the emission of greenhouse gases, has low reaction temperature and achieves the aims of energy conservation and emission reduction on the whole.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (2)

1. CO (carbon monoxide)2The preparation method of the furfural by hydrothermal liquefaction of agricultural and forestry waste under the atmosphere is characterized by comprising the following steps:
s1: collecting agricultural and forestry wastes, crushing and screening the agricultural and forestry wastes, adding the agricultural and forestry wastes into a hydrothermal reaction kettle, and mixing the agricultural and forestry wastes with deionized water to form mixed liquid; the grain size range of the agricultural and forestry waste is 60-120 meshes; the mass volume ratio of the mixed solution is 1: 5-1: 15; the agricultural and forestry waste comprises one or more of rice hulls, straws, corncobs or bamboo chips;
s2: with CO2Purging the kettle body, exhausting air in the reaction kettle, then closing the air outlet valve, and filling CO2Then, sealing the reaction kettle, heating the reaction kettle to 200 ℃ under stirring, and keeping the temperature for 10-50 minutes; the CO is2The pressure of the pressure is 1Mpa to 2 Mpa;
s3: cooling the hydrothermal reaction kettle to room temperature, decompressing and collecting gas, collecting a solid-liquid mixture after reaction in the reaction kettle, and performing vacuum filtration and separation on the solid-liquid mixture to obtain a solid part and a liquid part;
s4: and (3) extracting and extracting the liquid part obtained in the S3 by using an organic solvent, separating and filtering an organic phase, removing the organic solvent, and obtaining the biological oil rich in the furfural by rotary evaporation.
2. CO according to claim 12The method for preparing furfural by hydrothermal liquefaction of agricultural and forestry waste under the atmosphere is characterized in that in the step S4, the organic solvent comprises one or more of diethyl ether, dichloromethane or ethyl acetate.
CN201811594824.0A 2018-12-25 2018-12-25 CO (carbon monoxide)2Method for preparing furfural by hydrothermal liquefaction of agricultural and forestry waste under atmosphere Active CN109628128B (en)

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