CN105439994A - Method for preparing furfural from corncobs through microwave assisted SnCl4 catalysis - Google Patents
Method for preparing furfural from corncobs through microwave assisted SnCl4 catalysis Download PDFInfo
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- CN105439994A CN105439994A CN201511025656.XA CN201511025656A CN105439994A CN 105439994 A CN105439994 A CN 105439994A CN 201511025656 A CN201511025656 A CN 201511025656A CN 105439994 A CN105439994 A CN 105439994A
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- furfural
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- catalysis
- corn cob
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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
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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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- Physical Or Chemical Processes And Apparatus (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention belongs to the technical field of preparation of biomass chemicals and discloses a method for preparing furfural from corncobs through microwave assisted SnCl4 catalysis. The preparation method comprises steps as follows: degreased corncobs, a catalyst SnCl4 and water are added to a reactor and evenly mixed ultrasonically, then nitrogen is introduced at the microwave power of 400-600 W for oxygen removal, the mixture is heated by microwaves to the temperature of 160-190 DEG C for a reaction for 0-50 min, reaction products are separated and purified, and a product, namely, the furfural, is obtained. According to the method, the SnCl4 is used as the catalyst, the production of the furfural is highly selective, the catalytic efficiency is high, the environment-friendly effect is realized, corrosion is small, and the technological process is more environment-friendly; the reaction rate and the energy utilization rate are increased through microwave assisted heating, so that the reaction time is shortened, and the yield of the furfural is increased.
Description
Technical field
The invention belongs to biomass chemical preparing technical field, be specifically related to a kind of microwave-assisted SnCl
4catalysis corn cob prepares the method for furfural.
Background technology
Along with the exhaustion of fossil energy and oil fuel discharge are to the aggravation of earth climatic influences, exploring non-fossil energy has been the extremely urgent task of the universe.Biomass energy is wide as one distribution, total amount large, renewable and eco-friendly novel energy, has maximum compatibility, have maximum alternative potential to fossil energy with the industrial technology in modern times and modern life.
Furfural has another name called furtural, is the common industrial chemicals and the chemical solvents that come from biomass, is widely used in multiple field such as oil, chemical industry, medicine, agricultural chemicals, food and synthetic rubber, synthetic resins etc.First the commercial applications of furfural is realized in nineteen twenty-two by QuakerOats company.Up to now, at industrial scale, furfural can only be obtained by plant fiber material, is mainly rich in the lignocellulose of piperylene, as corn cob, bagasse, oat shell etc.Furfural has the character of the compounds such as aldehyde, ether, diolefine and aromatic hydrocarbon concurrently, and chemical property is active.Furfural can obtain more than 1600 kind of derivative through reactions such as oxidation, hydrogenation, chlorination, nitrated and condensations, and most of derivative overlaps with refinery products, can become the strong replacer of oil derived product.
The most promising starting material of furfural prepared by the wood fibre that wood fibre is particularly rich in wood sugar.But due to cell walls rigidity, compact structure, lignocellulose raw material has certain resistibility to biological degradation.Therefore, efficient preconditioning technique is developed most important for the development of furfural technique.Dilute acid pretreatment, as a kind of traditional commercial run, exists that equipment corrosion is serious, productive rate is low, produce the problems such as a large amount of trade effluents.Research shows, some generations of metal chloride to furfural with Lewis acidity have stronger catalytic activity, and there is the advantages such as catalytic efficiency is high, environmental friendliness, corrodibility are little, recyclable.Because lignocellulose raw material composition is various, complex structure, in hydrolytic process, diversified side reaction certainly will be there is, thus reduce furfural productive rate.
Summary of the invention
In order to solve the shortcoming and defect part of above prior art, the object of the invention is to a kind of microwave-assisted SnCl
4catalysis corn cob prepares the method for furfural.
The object of the invention is achieved through the following technical solutions:
A kind of microwave-assisted SnCl
4catalysis corn cob prepares the method for furfural, comprises following preparation process:
Add defatted corn core, catalyst S nCl in the reactor
4and water, ultrasonicly to mix, then under microwave power 400 ~ 600W condition, logical nitrogen deoxygenation, and microwave heating is warming up to 160 DEG C ~ 190 DEG C reaction 0 ~ 50min, reaction product, through separation and purification, obtains product furfural.
Preferably, described defatted corn core is by 40 ~ 80 order corn cobs acetone-ethanol (2:1, V/V) continuous extracting 6 ~ 8h in Soxhlet extractor, then obtains at 40 ~ 60 DEG C of drying 14 ~ 18h.
Preferably, the solid-to-liquid ratio of described defatted corn core and water is 1:(15 ~ 25) g/mL.
Preferably, described catalyst S nCl
4consumption be 10% ~ 20% of defatted corn core quality.
Preferably, the described ultrasonic time is 5 ~ 10min, and ultrasonic power is 30 ~ 40KHz.
Preferably, the time of described logical nitrogen deoxygenation is 5 ~ 10min.
Preferably, the process of described separation and purification is: with ice-water bath cooling, vacuum filtration, gained filtrate is through distillation and concentration, CH
2cl
2extraction and distillation, obtain product furfural.
Preferably, the productive rate of described furfural is 4.5wt% ~ 9.0wt%, and reaction residues mainly containing Mierocrystalline cellulose and xylogen, can be further used for the production of alcohol fuel.
Preparation method's tool of the present invention has the following advantages and beneficial effect:
(1) the present invention adopts SnCl
4as catalyzer, have higher selectivity to the generation of furfural, catalytic efficiency is high, environmental friendliness, corrodibility is little, technological process is environmental protection more;
(2) the present invention adopts the mode of Microwave-assisted firing to improve speed of reaction and capacity usage ratio, and then Reaction time shorten, to improve furfural productive rate;
(3) residue after corn cob catalysis of the present invention mainly contains Mierocrystalline cellulose and xylogen, and may be used for the production of the important biomolecule such as alcohol fuel, butanols fuel, the xylogen of acquisition may be used for industrial chemicals.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Following examples defatted corn core used prepares by the following method: by 40 ~ 80 order corn cobs acetone-ethanol (2:1, V/V) continuous extracting 7h in Soxhlet extractor, then obtain at 50 DEG C of dry 16h.
Following examples gained furfural detects mainly through high performance liquid chromatography, testing conditions is as follows: chromatographic column is WatersC18 post, column temperature is 30 DEG C, detector temperature is 30 DEG C, moving phase is acetonitrile: water=15:85 (V/V), the flow velocity of moving phase is 1.0mL/min, and sample size is 20 μ L.
Embodiment 1
A kind of microwave-assisted SnCl
4catalysis corn cob prepares the method for furfural, comprises the steps:
1.0g degreasing raw material corn cob, 0.1gSnCl is added in tetrafluoroethylene inner canister
4and the ultrapure water of 25mL.Tetrafluoroethylene inner canister is placed in ultrasonic cleaner ultrasonic 5min under 35KHz, make feed particles dispersed in water, infiltrate and get rid of the air in raw material space.Tetrafluoroethylene inner canister is inserted in PEEK outer tank tighten, loads microwave reaction instrument, insert sensor, pressure measurement nut of screwing on.The nitrogen of logical 7min is to displace oxygen in tank.Arranging temperature of reaction is 170 DEG C, heating-up time 14min, reaction times 0min, and power is 400W, adjusting rotary speed, starts reaction.
Get corn cob raw material, the SnCl of quality same as described above
4catalyzer and the water yield of identical solid-to-liquid ratio, be transferred in reaction under high pressure after same supersound process, the temperature and time that reacting phase is same.
After reaction terminates, retort/still is placed in ice-water bath and cools.After cooling, sample is used the G3 glass pot metre filter of constant weight.Get 1mL filtrate again via hole diameter be that the syringe filters of 0.22 μm is filtered laggard circumstances in which people get things ready for a trip spectrum and detected.By the described solution containing furfural through distillation and concentration, dichloromethane extraction and distillation, obtain product furfural.Filter residue obtained main containing Mierocrystalline cellulose and xylogen, both be separated further, the Mierocrystalline cellulose of acquisition may be used for producing the important biomolecule such as alcohol fuel, butanols fuel, and the xylogen of acquisition may be used for industrial chemicals.
Furfural percentage yield is calculated according to following formula:
Quality × 100% of furfural quality/over dry corn cob that furfural yield=HPLC records.
As calculated, in the present embodiment, under microwave-assisted condition, the yield of furfural is 6.5wt%; Under autoclave condition, furfural yield is 3.8wt%.Therefore the productive rate of microwave-assisted furfural is higher, and the reaction times is short, higher to furfural selectivity.
Embodiment 2
A kind of microwave-assisted SnCl
4catalysis corn cob prepares the method for furfural, comprises the steps:
1.0g degreasing raw material corn cob, 0.2gSnCl is added in tetrafluoroethylene inner canister
4and the ultrapure water of 15mL.Tetrafluoroethylene inner canister is placed in ultrasonic cleaner ultrasonic 8min under 40KHz, make feed particles dispersed in water, infiltrate and get rid of the air in raw material space.Tetrafluoroethylene inner canister is inserted in PEEK outer tank tighten, loads microwave reaction instrument, insert sensor, pressure measurement nut of screwing on.The nitrogen of logical 10min is to displace oxygen in tank.Arranging temperature of reaction is 180 DEG C, heating-up time 18min, reaction times 2.5min, and power is 500W, adjusting rotary speed, starts reaction.
Separately get 1.0g defatted corn core raw material, 0.2gSnCl
4catalyzer and 15mL ultrapure water, through 40KH
zultrasonic cleaning machine supersound process 8min after be transferred in autoclave, at 180 DEG C, react 2.5min.
After reaction terminates, retort/still is placed in ice-water bath and cools.After cooling, sample is used the G3 glass pot metre filter of constant weight.Get 1mL filtrate again via hole diameter be that the syringe filters of 0.22 μm is filtered laggard circumstances in which people get things ready for a trip spectrum and detected.By the described solution containing furfural through distillation and concentration, dichloromethane extraction and distillation, obtain product furfural.Filter residue obtained main containing Mierocrystalline cellulose and xylogen, both be separated further, the Mierocrystalline cellulose of acquisition may be used for producing the important biomolecule such as alcohol fuel, butanols fuel, and the xylogen of acquisition may be used for industrial chemicals.
As calculated, in the present embodiment, under microwave-assisted condition, the yield of furfural is 8.5wt%; Under autoclave condition, furfural yield is 4.3wt%.Therefore the productive rate of microwave assisting method furfural is higher, and the reaction times is short, higher to furfural selectivity.
Embodiment 3
A kind of microwave-assisted SnCl
4catalysis corn cob prepares the method for furfural, comprises the steps:
By 1g defatted corn core, 20mL ultrapure water and 0.1gSnCl
4join in tetrafluoroethylene inner canister, and be ultrasonic 10min in the ultrasonic cleaning machine of 30KHz with power.After being loaded microwave reaction instrument, pass into 8min nitrogen to remove the oxygen in container.Microwave reaction condition is as follows: temperature of reaction 190 DEG C, heating-up time 21min, reaction times 0min, microwave power 600W.
Under the condition that corn cob quality, catalyst levels and solid-to-liquid ratio are all same as described above, after same power and the supersound process of time, mixed solution is transferred to autoclave, carries out catalyzed reaction with identical temperature and time.
After reaction terminates, retort/still is placed in ice-water bath and cools rapidly, with G3 funnel vacuum filtration, gets 1mL filtrate and measure its furfural content, through remaining filtrate through distillation and concentration, dichloromethane extraction and distillation, obtain product furfural.Residue obtained main containing Mierocrystalline cellulose and xylogen, both be separated further, gained Mierocrystalline cellulose is used for the production of the biofuel such as alcohol fuel, butanols, and xylogen may be used for industrial chemicals.
As calculated, in the present embodiment, under microwave-assisted condition, the yield of furfural is 9.0wt%; Under autoclave condition, furfural yield is 3.5wt%.Therefore the productive rate of microwave assisting method furfural is higher, and the reaction times is short, higher to furfural selectivity.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. a microwave-assisted SnCl
4catalysis corn cob prepares the method for furfural, it is characterized in that comprising following preparation process:
Add defatted corn core, catalyst S nCl in the reactor
4and water, ultrasonicly to mix, then under microwave power 400 ~ 600W condition, logical nitrogen deoxygenation, and microwave heating is warming up to 160 DEG C ~ 190 DEG C reaction 0 ~ 50min, reaction product, through separation and purification, obtains product furfural.
2. a kind of microwave-assisted SnCl according to claim 1
4catalysis corn cob prepares the method for furfural, it is characterized in that: described defatted corn core is acetone-ethanol continuous extracting 6 ~ 8h in Soxhlet extractor of 2:1 by 40 ~ 80 order corn cob volume ratios, then obtains at 40 ~ 60 DEG C of drying 14 ~ 18h.
3. a kind of microwave-assisted SnCl according to claim 1
4catalysis corn cob prepares the method for furfural, it is characterized in that: the solid-to-liquid ratio of described defatted corn core and water is 1:(15 ~ 25) g/mL.
4. a kind of microwave-assisted SnCl according to claim 1
4catalysis corn cob prepares the method for furfural, it is characterized in that: described catalyst S nCl
4consumption be 10% ~ 20% of defatted corn core quality.
5. a kind of microwave-assisted SnCl according to claim 1
4catalysis corn cob prepares the method for furfural, it is characterized in that: the described ultrasonic time is 5 ~ 10min, and ultrasonic power is 30 ~ 40KHz.
6. a kind of microwave-assisted SnCl according to claim 1
4catalysis corn cob prepares the method for furfural, it is characterized in that: the time of described logical nitrogen deoxygenation is 5 ~ 10min.
7. a kind of microwave-assisted SnCl according to claim 1
4catalysis corn cob prepares the method for furfural, it is characterized in that the process of described separation and purification is: with ice-water bath cooling, vacuum filtration, gained filtrate is through distillation and concentration, CH
2cl
2extraction and distillation, obtain product furfural.
8. a kind of microwave-assisted SnCl according to claim 1
4catalysis corn cob prepares the method for furfural, it is characterized in that: the productive rate of described furfural is 4.5wt% ~ 9.0wt%, and reaction residues is further used for the production of alcohol fuel.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511025656.XA CN105439994B (en) | 2015-12-29 | 2015-12-29 | A kind of method that microwave radiation technology SnCl4 catalysis corncob prepares furfural |
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|---|---|---|---|
| CN201511025656.XA CN105439994B (en) | 2015-12-29 | 2015-12-29 | A kind of method that microwave radiation technology SnCl4 catalysis corncob prepares furfural |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112028861A (en) * | 2020-09-01 | 2020-12-04 | 吉林大学 | Method for preparing furfural by catalyzing corncobs |
| CN115819380A (en) * | 2022-11-16 | 2023-03-21 | 安徽金禾化学材料研究所有限公司 | Neutral gas explosion-SO 3 Method for preparing furfural by catalyzing corn cob through ultrasonic coupling pretreatment |
-
2015
- 2015-12-29 CN CN201511025656.XA patent/CN105439994B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| RISTINA SÁNCHEZ ET AL.: "Furfural production from corn cobs autohydrolysis liquors by microwave technology", 《INDUSTRIAL CROPS AND PRODUCTS》 * |
| WENJU WANG ET AL.: "Direct transformation of xylan-type hemicelluloses to furfural via SnCl4 catalysts in aqueous and biphasic systems", 《BIORESOURCE TECHNOLOGY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112028861A (en) * | 2020-09-01 | 2020-12-04 | 吉林大学 | Method for preparing furfural by catalyzing corncobs |
| CN112028861B (en) * | 2020-09-01 | 2023-06-27 | 吉林大学 | Method for preparing furfural by catalyzing corncob |
| CN115819380A (en) * | 2022-11-16 | 2023-03-21 | 安徽金禾化学材料研究所有限公司 | Neutral gas explosion-SO 3 Method for preparing furfural by catalyzing corn cob through ultrasonic coupling pretreatment |
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| CN105439994B (en) | 2017-12-01 |
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