CN101633651B - Method for preparing furfuraldehyde directly from water washing substances of steam explosion through acidless autocatalysis - Google Patents
Method for preparing furfuraldehyde directly from water washing substances of steam explosion through acidless autocatalysis Download PDFInfo
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- CN101633651B CN101633651B CN2008101344218A CN200810134421A CN101633651B CN 101633651 B CN101633651 B CN 101633651B CN 2008101344218 A CN2008101344218 A CN 2008101344218A CN 200810134421 A CN200810134421 A CN 200810134421A CN 101633651 B CN101633651 B CN 101633651B
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Abstract
The invention belongs to the field of comprehensive utilization of crop straw resources. Aiming at a scheme that the conventional furfuraldehyde preparing process has high energy consumption, and acid is added to cause pollution and no economy, the invention provides a novel process for preparing furfuraldehyde directly from water washing substances of steam exploded crop straw resources through acidless autocatalysis. A series of crop straw resources such as maize straw, wheat straw, rice hulls and the like are subjected to steam explosion, and are subjected to water washing by hot water in a certain mode; the water washing substances rich in sugar are maintained; the water washing substances after filtration and concentration are not additionally added with acid, but are directly prepared into the furfuraldehyde through acid generated in the steam explosion process. The steam explosion treatment process makes structures of materials dispersed and fibers fully exposed, and provides convenience for subsequent value-added treatment such as enzymolysis and fermentation, and the like on the steam exploded materials, so the crop resources can be reasonably utilized in grades and levels.
Description
Technical field
The invention belongs to the comprehensive utilization of crop straw resources field, relate to the Technology that the agricultural straw resource layered multi-stage transforms coproduction system furfural, be focussed in particular on the method that the autocatalysis of agricultural crop straw water washing substances of steam explosion anacidity directly prepares furfural.
Background technology
China is a large agricultural country, and all kinds of agronomic crop fibre resources are very abundant.Common have maize straw, rice husk, a wheat straw etc.Wherein only one of stalk just reaches more than 7.0 * 109kg, the about 2.2 * 1011kg of maize straw wherein, and these resource long-terms are not reasonably developed.At China's southern area, the by product after the rice is taken off in the rice husk conduct, mainly is used as feed burning etc.It is reported that the content of hemicellulose is up to 19% in the rice husk.In addition, because the rice husk volume is little, the production that can directly feed intake, and also the rice threshing generally concentrates on threshing factory, and raw material is convenient to concentric acquisition, if its utilization can there be very wide prospect.How material as agricultural wastes is burnt with fuel, contains a large amount of TSP and SO in its smog
2, cause the atmosphere severe contamination.The research of biomass energy has in recent years become the research topic of a hot topic, utilizes the comprehensive utilization of agricultural wastes just progressively to become the focus that people study.
China's agricultural wastes are except small part is utilized, and major part cause very big pollution and waste, and this direct incendiary method thermo-efficiency is very low with direct impouring environment of form such as accumulation, waste burnings, has only about 10%.Agricultural wastes such as wheat straw; maize straw; major parts such as rice husk all contain abundant Mierocrystalline cellulose; hemicellulose is if the utilization of science in addition can be turned waste into wealth; alleviate the human crisis of resource that is faced; be short of food, a series of problems such as environmental pollution also provide assurance for human sustainable development.With the maize straw be example it mainly form by plant cell wall, the cell walls essentially consist is Mierocrystalline cellulose, hemicellulose, xylogen, Mierocrystalline cellulose and hemicellulose are wrapped up layer by layer by xylogen, Mierocrystalline cellulose is that a kind of 1000-10000 of having β-D glucopyranose monomer is with β-1, the straight-chain polysaccharide that 4 glycosidic links connect, a plurality of molecule parllels are arranged in thread insoluble micro fiber, and its essentially consist unit is a cellobiose, and it is a polymer the abundantest on the earth.And hemicellulose mainly is wood sugar and a small amount of pectinose, semi-lactosi, and seminose is formed, and xylogen is to be the polymer aromatics of fundamental unit formation with phenylpropyl alcohol alkane and derivative thereof, and hydrocellulose is played barrier action.Up to the present, also find to utilize the microorganism of single aggressiveness producing and ethanol in next life of xylogen.Hemicellulose is a five-carbon sugar than facile hydrolysis, and Mierocrystalline cellulose difficulty is hydrolyzed to hexose, and xylogen generally acts as a fuel.Utilize the technology of the cellulase hydrolysis preparing fuel ethanol in the maize straw to cause attention widely at present, and reach its maturity.This patent also belongs to the agricultural resource general field.
As far back as 1821, Doebernier at first found furfural, and subsequently, people have carried out deep research to its physicochemical property and synthetic method thereof.Nineteen twenty-two, U.S. Quaker Oats company has at first realized the industrialization of furfural, is mainly used in wood rosin decolouring and lube oil finishing aspect, has realized the application of furfural at industrial circle; The forties in 20th century, furfural is widely used in fields such as synthetic rubber, medicine, agricultural chemicals; After the sixties,, greatly promoted the development of furfurol industry along with the exploitation of furfural derivatives, particularly furane resin widespread use at foundry industry; After the seventies,, utilize the furfural of reproducible agriculture forestry waste production high added value, and develop its downstream Chemicals and be subjected to people and more and more pay attention to along with the rise of energy dilemma and oil price.
The pure product of furfural are water white liquid, and the stimulation gas with similar Prunus amygdalus oil is hidden, and contacts with air. when particularly in furfural acid being arranged, the meeting autoxidation becomes dark brown bag gradually, even becomes the chocolate resinous substance.Furfural can be dissolved in a lot of organic solvents: as alcohol, acetone, ether, acetic acid, benzene and tetracol phenixin.A furan nucleus and an aldehyde radical are arranged in the furfural molecular structure. furan ticks to encircle two two keys and cyclic ethers key again, reactions such as hydrogenation, oxidation, chlorination, nitrated and contracting can take place. thereby can prepare a large amount of derived products, so furfural is a kind of important Organic Chemicals again. can be used for a large amount of fine chemical products such as synthetic pesticide, medicine, dyestuff, coating, resin.
Furfural has another name called furtural, be a kind of important Organic Chemicals and chemical solvents that is widely used in industries such as refining of petroleum, petrochemical complex, chemical industry, medicine, food and synthetic rubber, synthetic resins, can only make by hydrolysis by plant fiber material up to now.Furfural not only can prepare important Organic Chemicals such as furfuryl alcohol, furans, tetrahydrofuran (THF), cis-butenedioic anhydride, furancarboxylic acid. but also become industry such as rubber, medicine, agricultural chemicals, oil fine jade system, dyestuff, spices that purposes is widely arranged at synthetic resins, synthon, platform.Many at present bibliographical informations about the furfural preparation, as CN87100099CN1616443 CN101113145 CN1381450 etc., use diluted acid catalysis system furfural (as sulfuric acid, hydrochloric acid etc.) but all concentrate on, directly do not produce the technology of furfural and rarely have report and do not add acid catalysis.
Summary of the invention
Main purpose of the present invention is exactly to carry out environmental protection, high-valued utilization at the quick-fried water lotion of vapour, has developed the technology of utilizing of water lotion after utilizing that vapour is quick-fried and finishing, obtains purpose product furfural.A part of hemicellulose of degrading in the quick-fried process of vapour is converted into five-carbon sugars such as wood sugar, water lotion is not added organic or mineral acid to be utilized arboxylic acid of producing in the quick-fried process of vapour etc. to make catalyzer to come catalyzed reaction directly to produce furfural, pollutions such as adding various acids in traditional system furfural process, single shortcoming have been overcome.Another object of the present invention provides a kind of system process of implementing the inventive method.
Processing step of the present invention is as follows:
(1) to maize straw, wheat straw, raw materials such as rice husk carry out the steam explosion pre-treatment, wash then, behind the washing filtering concentrating under reduced pressure, so that next step preparation furfural;
(2) reaction solution after will handling adds in the reactor, does not additionally add acid, in 150～180 ℃ of reaction 2-5h, after reaching temperature of reaction, slowly open steam valve, open condensing works the furfural condensing reflux is come out, this step system be the aldehyde water mixed liquid, be referred to as thick aldehyde; After slightly the certain alkali lye of aldehyde aqueous solution interpolation neutralizes its pH value, add in the refining kettle thick aldehyde is made with extra care, make furfural and high cut resinifying separating substances.
The method that described vapour is quick-fried, maize straw, wheat straw, agriculture waste raw material steam explosion pre-treatment pressure such as rice husk are at 1.1MPa～1.7MPa, and keeping pressure time is 3 minutes～10 minutes.
Described washing is added 70～90 ℃ of water of 2～3 times after to be that vapour is quick-fried finish in material, fully stir back centrifuging and taking supernatant liquor about 15min, filters once more after getting supernatant liquor; Water lotion underpressure distillation with after filtering steams moisture wherein, concentrates 4～5 times.
Advantage of the present invention is 1. material to be carried out the steam explosion pre-treatment, has increased the degree of scatter of its fiber greatly, helps next step processing such as enzymatic hydrolysis and fermentation etc. of material.2. gas-explosive material is washed, the acid of the quick-fried generation of flush away vapour, sugar, compositions such as leachable thing, help the separation of its long and short fiber, be convenient to long and short fiber and utilize targetedly, through the material after the washing, the inhibition composition that wherein is unfavorable for enzymatic hydrolysis and fermentation also significantly reduces, and is convenient to the further utilization of material.3. water washing substances directly produce the furfural step different with a certain amount of acid of traditional interpolation be to utilize the acid that vapour produces in quick-fried and do not add extra acid, economic environmental protection.4. the present invention utilizes the water washing substances of steam explosion anacidity directly to produce the technology of furfural, novelty, and uniqueness has originality, for producing of furfural opened up new approaches.
Description of drawings
The quick-fried water lotion anacidity of Fig. 1 vapour autocatalysis system furfural production technology.
Fig. 2 is a techniqueflow system diagram of the present invention
Embodiment
Embodiment 1
1. after wheat straw waste being purified, be crushed to the length of 3-4cm after, add the moistening material of water with 1: 1 solid-to-liquid ratio and put behind the 0.5h stand-by.2. pretreated wheat straw waste is carried out the quick-fried processing of vapour, vapour detonation pressure power about 1.4MPa, the quick-fried time 4min of vapour.3. vapour is quick-fried finish after, in 1: 3 solid-liquid ratio add about 80 ℃ hot water so that wood sugar can wash out more completely.Material after vapour is quick-fried can be used for further processing such as enzymatic hydrolysis and fermentation, and the quick-fried water lotion of vapour is used to produce the further experiment of furfural.4. the quick-fried water lotion of vapour is further processed, water lotion is centrifugal, and 4-5 doubly concentrates behind the suction filtration, and the xylose concentration in the water lotion is improved.5. anacidity autocatalysis system furfural under the high-temperature and high-pressure conditions: get the water lotion after 100ml concentrates, add reaction kettle for reaction, wait (about 1h) unlatching vapour phase valve after 160 ℃ of the temperature of reaction that reach setting, vapor condensation is collected out, collect 2h, collect the phlegma of about 75ml, detect.
The gained index is as follows:
| Initial wood sugar content | Initial formic acid content | Initial acetic acid content | The xylose utilization amount | The furfural transformation efficiency | Reaction beginning pH | Reaction finishes pH |
| 31.72g/L | 400.03mg/L | 441.02mg/L | 2.781g | 30.50％ | 4.3 | 3.6 |
Embodiment 2
1. after maize straw being purified, be crushed to the length of 5-10cm after, add the moistening material of water with 1: 1 solid-to-liquid ratio, place behind the 0.5h stand-by.2. pretreated maize straw is carried out the quick-fried processing of vapour, vapour detonation pressure power about 1.5MPa, the quick-fried time 5min of vapour.3. vapour is quick-fried finish after, in 1: 2 solid-liquid ratio add about 80 ℃ hot water so that wood sugar can wash out more completely.Material after vapour is quick-fried can be used for further processing such as enzymatic hydrolysis and fermentation, and the quick-fried water lotion of vapour is used to produce the further experiment of furfural.4. the quick-fried water lotion of vapour is further processed, water lotion is centrifugal, and 4-5 doubly concentrates behind the suction filtration, and the xylose concentration in the water lotion is improved.5. anacidity autocatalysis system furfural under the high-temperature and high-pressure conditions: get the water lotion after 100ml concentrates, add reaction kettle for reaction, wait (about 1h) unlatching vapour phase valve after 170 ℃ of the temperature of reaction that reach setting, vapor condensation is collected out, collect 2h, collect the phlegma of about 75ml, detect.
The gained index is as follows:
| Initial wood sugar content | Initial formic acid content | Initial acetic acid content | The xylose utilization amount | The furfural transformation efficiency | Reaction beginning pH | Reaction finishes pH |
| 38.48g/L | 450.21mg/L | 460.79mg/L | 3.526g | 36.90％ | 3.9 | 3.4 |
Embodiment 3
1. after maize straw being purified, be crushed to the length of 5-10cm after, add the moistening material of water with 1: 1 solid-to-liquid ratio, place behind the 1h stand-by.2. pretreated maize straw is carried out the quick-fried processing of vapour, vapour detonation pressure power about 1.4MPa, the quick-fried time 5min of vapour.3. vapour is quick-fried finish after, in 1: 3 solid-liquid ratio add about 80 ℃ hot water so that wood sugar can wash out more completely.Material after vapour is quick-fried can be used for further processing such as enzymatic hydrolysis and fermentation, and the quick-fried water lotion of vapour is used to produce the further experiment of furfural.4. the quick-fried water lotion of vapour is further processed, water lotion is centrifugal, and 4-5 doubly concentrates behind the suction filtration, and the xylose concentration in the water lotion is improved.5. anacidity autocatalysis system furfural under the high-temperature and high-pressure conditions: get the water lotion after 100ml concentrates, add reaction kettle for reaction, wait (about 1h) unlatching vapour phase valve after 180 ℃ of the temperature of reaction that reach setting, vapor condensation is collected out, collect 2h, collect the phlegma of about 75ml, detect.
The gained index is as follows:
| Initial wood sugar content | Initial formic acid content | Initial acetic acid content | The xylose utilization amount | The furfural transformation efficiency | Reaction beginning pH | Reaction finishes pH |
| 35.36g/L | 437.28mg/L | 423.65mg/L | 3.133g | 33.21％ | 3.9 | 3.4 |
Embodiment 4:
1. after rice husk being purified, add the moistening material of water with 1: 1 solid-to-liquid ratio, stand-by behind the placement 1h.2. pretreated rice husk is carried out the quick-fried processing of vapour, vapour detonation pressure power about 1.3MPa, the quick-fried time 4min of vapour.3. vapour is quick-fried finish after, in 1: 2 solid-liquid ratio add about 80 ℃ hot water so that wood sugar can wash out more completely.Material after vapour is quick-fried can be used for further processing such as enzymatic hydrolysis and fermentation, and the quick-fried water lotion of vapour is used to produce the further experiment of furfural.4. the quick-fried water lotion of vapour is further processed, water lotion is centrifugal, and 4-5 doubly concentrates behind the suction filtration, and the xylose concentration in the water lotion is improved.5. anacidity autocatalysis system furfural under the high-temperature and high-pressure conditions: get the water lotion after 100ml concentrates, add reaction kettle for reaction, open the vapour phase valve Deng (about 1h) after 10 ℃ of the temperature of reaction that reaches setting, vapor condensation is collected out, collect 2h, collect the phlegma of about 75ml, detect, the gained index is as follows:
| Initial wood sugar content | Initial formic acid content | Initial acetic acid content | The xylose utilization amount | The furfural transformation efficiency | Reaction beginning pH | Reaction finishes pH |
| 29.44g/L | 354.82mg/L | 329.60mg/L | 2.641g | 29.21％ | 4.5 | 4.1 |
Claims (3)
1. the processing method of the quick-fried water lotion anacidity of a vapour autocatalysis system furfural, its step is as follows:
(1) maize straw, wheat straw, rice husk are carried out the steam explosion pre-treatment, wash then, water lotion is filtered concentrating under reduced pressure after so that next step the preparation furfural;
(2) reaction solution after will handling adds in the reactor, does not additionally add acid, in 150～180 ℃ of reaction 2-5h, after reaching temperature of reaction, slowly open steam valve, open condensing works the furfural condensing reflux is come out, this step system be the aldehyde water mixed liquid, be referred to as thick aldehyde; After slightly the certain alkali lye of aldehyde aqueous solution interpolation neutralizes its pH value, add in the refining kettle thick aldehyde is made with extra care, make furfural and high cut resinifying separating substances.
2. by the method described in the claim 1, it is characterized in that: the described maize straw of step (1), wheat straw, rice husk steam explosion pre-treatment pressure are at 1.1MPa～1.7MPa, and keeping pressure time is 3 minutes～10 minutes.
3. by the method described in the claim 1, it is characterized in that: the described washing of step (1) is added 70～90 ℃ of water of 2～3 times after to be that vapour is quick-fried finish in material, fully stirs centrifuging and taking supernatant liquor behind the 15min, filters once more after getting supernatant liquor; Water lotion underpressure distillation with after filtering steams moisture wherein, concentrates 4～5 times.
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| CN102391217A (en) * | 2011-12-06 | 2012-03-28 | 中国科学院过程工程研究所 | Method for preparing furaldehyde from steam exploded stalk rinse solution catalyzed by using solid acid with added polymerization inhibitor |
| CN105418553A (en) * | 2015-11-24 | 2016-03-23 | 滁州市润达溶剂有限公司 | Method for preparing furfural through steam explosion separation method |
| CN110563675B (en) * | 2019-08-01 | 2023-05-30 | 四川金象赛瑞化工股份有限公司 | Method for preparing furfural and fully utilizing xylose by cotton stalk steam explosion extraction |
| CN111115640B (en) * | 2020-01-03 | 2022-05-31 | 吉林大学 | Method for preparing natural nano silicon dioxide and comprehensively utilizing rice hulls |
| CN113861439B (en) * | 2021-09-18 | 2024-01-02 | 四川金象赛瑞化工股份有限公司 | Continuous sulfonation process of sulfur trioxide from plant straw |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381450A (en) * | 2001-04-17 | 2002-11-27 | 上海长洁卫生保健制品有限公司 | Process for preparing glycoaldehyde from cane dregs |
| CN1616443A (en) * | 2004-09-27 | 2005-05-18 | 王�义 | Process and device for producing furol by two step continuous low pressure high temperature dynamic hydrolysis method |
| CN101113145A (en) * | 2006-07-25 | 2008-01-30 | 孙新龙 | Process for producing furfuraldehyde by corn and corn fabric by corn polyalcohol |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381450A (en) * | 2001-04-17 | 2002-11-27 | 上海长洁卫生保健制品有限公司 | Process for preparing glycoaldehyde from cane dregs |
| CN1616443A (en) * | 2004-09-27 | 2005-05-18 | 王�义 | Process and device for producing furol by two step continuous low pressure high temperature dynamic hydrolysis method |
| CN101113145A (en) * | 2006-07-25 | 2008-01-30 | 孙新龙 | Process for producing furfuraldehyde by corn and corn fabric by corn polyalcohol |
Non-Patent Citations (1)
| Title |
|---|
| 陈洪章等.无污染秸秆汽爆新技术及其应用.《纤维素科学与技术》.2002,第10卷(第3期),47-52. * |
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