CN102617523B - Method for preparing 5-hydroxymethylfurfural by hydrothermally decomposing wood fibers - Google Patents
Method for preparing 5-hydroxymethylfurfural by hydrothermally decomposing wood fibers Download PDFInfo
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 62
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 31
- 229920002522 Wood fibre Polymers 0.000 title claims abstract description 26
- 239000002025 wood fiber Substances 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000012074 organic phase Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 24
- 229920002678 cellulose Polymers 0.000 claims description 23
- 239000001913 cellulose Substances 0.000 claims description 23
- 239000012043 crude product Substances 0.000 claims description 15
- 238000001704 evaporation Methods 0.000 claims description 13
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- 238000009413 insulation Methods 0.000 claims description 13
- 239000010902 straw Substances 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 241000209094 Oryza Species 0.000 claims description 6
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- 235000009566 rice Nutrition 0.000 claims description 6
- 229920002488 Hemicellulose Polymers 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 abstract description 16
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- 229920000742 Cotton Polymers 0.000 description 36
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 23
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 23
- 235000010980 cellulose Nutrition 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000004128 high performance liquid chromatography Methods 0.000 description 13
- 239000011973 solid acid Substances 0.000 description 8
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
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- 229930091371 Fructose Natural products 0.000 description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 3
- 239000005715 Fructose Substances 0.000 description 3
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
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- 150000004676 glycans Chemical class 0.000 description 2
- 150000002402 hexoses Chemical class 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
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- 239000002023 wood Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- -1 cornstalk Substances 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
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- 229940040102 levulinic acid Drugs 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- YPJJABHAGGFGAM-UHFFFAOYSA-M lithium;n,n-dimethylacetamide;chloride Chemical compound [Li+].[Cl-].CN(C)C(C)=O YPJJABHAGGFGAM-UHFFFAOYSA-M 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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Abstract
The invention discloses a method for preparing 5-hydroxymethylfurfural by hydrothermally decomposing wood fibers, which comprises the following steps: drying and pulverizing wood fibers to 40-120 meshes, soaking with water, treating with an ultrasonic apparatus for 5-20 minutes, mixing with a catalyst and a solvent, and stirring to carry out hydrolysis reaction at 170-250 DEG C for 30-150 minutes; after the reaction finishes, cooling and filtering; extracting the water phase with an organic solvent, merging the extraction liquid and the organic phase, and removing the solvent to obtain the 5-hydroxymethylfurfural. The invention has the advantages of cheap and accessible raw material and abundant sources, can solve the problem of raw material sources of 5-hydroxymethylfurfural, relieves the environmental pollution from stacked waste wood fibers, and enhances the wood fiber hydrolysis efficiency by using ultrasonic processing.
Description
Technical field:
The present invention relates to a kind of method of being prepared 5 hydroxymethyl furfural by wood fibre, particularly a kind of wood fibre hydrothermal decomposition after supersound process is prepared the method for 5 hydroxymethyl furfural.
Background technology:
In 5 hydroxymethyl furfural (5-HMF) molecule, contain an aldehyde radical and a methylol, can pass through hydrogenation, oxydehydrogenation, esterification, halogenation, polymerization, hydrolysis and other chemical reaction, for the synthesis of many useful compounds and novel high polymer material, it is a kind of important hardware and software platform compound.Take 5-HMF as the synthetic biomass liquid fuel 2 similar to ethanol of raw material, 5-dimethyl furan, its energy density is higher by 40% than ethanol, and boiling point is high 20 ℃, is a kind of than the more preferably new forms of energy material of substitute fossil fuels of ethanol.
The raw material that traditional method of preparing 5-HMF adopts is fructose, and the people such as James A Dumesic (Nature, 2007,447, the solution selectively dewatering of 914-915) having studied high fructose concentration generates the method for 5-HMF, and product yield is up to 80%.But the service cost of fructose is higher, be unfavorable for the large-scale industrial production of 5-HMF.In recent years, mostly the preparation of 5-HMF is that polysaccharide or the Microcrystalline Cellulose of take hexose or having hexose structure are raw material.Polysaccharide or Mierocrystalline cellulose are hydrolyzed and generate monose under acidic conditions, and then monose further dewaters and generates 5-HMF.The people such as the Hou Xianglin of Shanxi Coal-Chemical Inst., Chinese Academy of Sciences (CN101948452) have studied take Mierocrystalline cellulose and prepares the method for 5-HMF as raw material.Raw material be take mass ratio and is mixed as 1: 3～10 with water, temperature of reaction is 120～250 ℃, and by Liquid carbon dioxide injecting reactor, control reaction pressure is 10～25MPa, and productive rate is between 50%～80%.Because 5-HMF only has good solubility property at supercritical co in mutually, so the method need to be reacted under condition of high voltage, condition is harsh, high to equipment requirements.
Adopt large, the inexpensive lignocellulose of storage capacity as raw material, can effectively reduce the production cost of 5-HMF, also can slow down these lignocellulose wastes and directly pile the environmental stress that existence brings.Joseph Bartholomew BINDER etc. (US2010/0004437A1) disclose usings the multiple lignocelluloses such as cornstalk, pine sawdust and as raw material, generates the method for 5-HMF, has adopted DMA-LiCl mixed system, adds CrCl
2or CrCl
3as metal catalyst, and optionally add mineral acid, metal halide or ionic liquid as additive, under the condition of 80～140 ℃, react 1h～24h, the molar yield that detection can obtain 5-HMF through HPLC is between 10%～48%.But this method has adopted chromic salts as catalyzer, also have certain additive, reaction system is more complicated also, is unfavorable for separation and the industrialization of product.The Hu Suqin of Inst. of Energy, Shandong Prov. Academy etc. (CN101935312) utilize starch for the mixed system of raw material employing water and organic solvent, under the effect of an acidic catalysts such as mineral acid and Zeo-karb and zeolite, reaction preparation 5-HMF, obtains the productive rate of target product based on synanthrin between 30%～65%.The shortcoming of these methods is that the mineral acid adopting has certain corrodibility to equipment, acid-bearing wastewater is not easy to reclaim, and the catalytic effect that the temperature range of the solid acid catalysis hydrolysis such as ion exchange resin just can play 130 ℃ of left and right, and because Mierocrystalline cellulose has very high degree of crystallinity, Mierocrystalline cellulose reactive behavior in conventional solvent is very low.Therefore, find the key that comparatively cheap bulk raw material and more economical efficient production technique become preparation 5-HMF.
Summary of the invention
The object of this invention is to provide that a kind of to take the wood fibre of discarding be raw material, utilize supersound process, the method for 5-HMF is prepared in High-efficient Water thermolysis.The wood fibres such as cotton stalk are after ultrasonic pretreatment, and the crystal region that aqueous solvent molecule is more easily penetrated in fibrous texture makes hydroxyl fracture, improve the yield of cellulosic molecule hydrolysis preparation 5-HMF.This method raw material sources are extensive, and cellulose decomposition efficiency is high.
For realizing above-mentioned object, the method applied in the present invention is as follows:
Wood fibre hydrothermal decomposition is prepared a method for 5 hydroxymethyl furfural, comprises the following steps:
1) by wood fibre through super-dry, be crushed to 40～120 orders;
2) by step 1) wood fiber powder after the pulverizing that obtains mixes through supersound process with the mixed system of water with catalyzer, organic solvent; Described catalyzer is solid acid catalyst;
3) by step 2) mixture hydrolysis reaction 30～150min at the temperature of 170～250 ℃ of obtaining;
4) hydrolysis reaction removes by filter residue and catalyzer after completing, organic solvent methyl iso-butyl ketone (MIBK) MIBK extraction for the water of the hydrolyzed solution obtaining, and the organic phase merging of extraction phase and hydrolyzed solution, obtains 5 hydroxymethyl furfural crude product after removing organic solvent.After removing solvent by evaporation, obtain 5-HMF crude product, then obtain 5-HMF sterling with ethyl alcohol recrystallization.
Above-mentioned steps 2) another kind of processing mode is: the part or all of water in the mixed system of organic solvent and water is first joined to step 1) in wood fiber powder after pulverizing, after supersound process, then add catalyzer, organic solvent to mix with the remainder of the mixed system of water.
Described wood fibre comprises one or more in cotton stalk, straw, rice straw, cornstalk, wood chip or other discarded wood fibre.
Step 2) the described supersound process time is 5-20 minute.
Step 2) described organic solvent and the mixed system of water: wood fibre mass ratio is 30: 1～150: 1.
Step 2) described organic solvent comprises propyl carbinol, methyl iso-butyl ketone (MIBK) MIBK or dimethyl sulfoxide (DMSO) DMSO.
Step 2) in the mixed system of described organic solvent and water, the volume ratio of organic solvent and water is 5: 1～1: 1.
Step 2) described solid acid catalyst comprises HZSM molecular sieve or MCM-41 molecular sieve.
Described solid acid catalyst accounts for 0.1%～10% of wood fiber powder quality.
Beneficial effect of the present invention:
1) wood fibre, after pulverizing reacts under higher temperature conditions, and the hemicellulose in raw material and Mierocrystalline cellulose can fully be hydrolyzed generation monose, and then monose continues hydrolysis generation 5-HMF under acidic conditions.Temperature of reaction is selected 170～250 ℃, and temperature of reaction is too low, and wood fibre is difficult for decomposing, and cellulosic crystalline texture is difficult for destroyed, causes cellulosic low conversion rate.Along with the increase of temperature of reaction, the speed that cellulose hydrolysis is monose is accelerated, and is further hydrolyzed to again in a short period of time 5-HMF.But excess Temperature, wood fibre charing is serious, and 5-HMF can continue again to decompose by products such as generating levulinic acid.Therefore it is very necessary selecting a suitable temperature.
2), because the 5-HMF generating in reaction is easy to and water generation hydration reaction in water, generate the by products such as formic acid, had a strong impact on the yield of 5-HMF.The present invention has adopted the two-phase system of water-organic solvent, makes to decompose the 5-HMF producing and is extracted to soon in organic phase, so can suppress to a certain extent the hydration reaction of target product, to improving yield, has certain help.
3) what, the present invention preferably adopted is that the solid acid catalysts such as HZSM carry out catalysis, contrast adopt mineral acid, lewis acid as the catalytic effect of catalyzer than solid acid catalyst slightly a little less than, and today of being rooted in the hearts of the people gradually in the concept of environmental consciousness and " Green Chemistry ", the water-fast solid acid catalyst that we adopt not only has good selectivity to 5-HMF, be easy to separation, nor easily cause the corrosion of equipment, be a kind of eco-friendly catalyzer.
4) raw material that, the present invention adopts is wood fibre cheap and easy to get, reduced raw materials cost, and the realization of this invention both can solve in rural area wood fibre and arbitrarily stacked caused environmental problem, can also partly replace petroleum chemicals, there is very important using value.
5) the present invention improves the wood fibre that the measure of yield is the pulverizing of employing supersound process process most, destroys cellulosic high-crystallinity in wood fibre, improves cellulosic reactive behavior.
Embodiment:
Below in conjunction with specific embodiment, the present invention is further illustrated, but be not restriction the present invention.
Embodiment 1:
By dried cotton stalk crushing, to 40-120 order, (in butt, cellulose 40.8%, hemicellulose 15.7%, xylogen 10.23%, ash content 0.17%), by suitable quantity of water, soak, put into ultrasonic apparatus supersound process 40kHz, 10 minutes, the water that adds 1: 1: MIBK mixed solvent, solvent adding amount is the weight (comprising the water yield that supersound process adds) of 50 times of cotton stalk powders, 5% (with cotton stalk powder weighing scale) HZSM molecular sieve catalyst is put into autoclave together, setting temperature of reaction is 210 ℃, adopt the temperature rise rate of 10K/min when temperature is raised to preset temp, insulation hydrolysis reaction 90min, reaction finishes rear taking-up kettle and carries out cooling, and then filtration residue obtains cotton stalk hydrolyzed solution.After the water of hydrolyzed solution extracts with MIBK, then merge with the organic phase of hydrolyzed solution, after solvent is removed in evaporation, obtain 5-HMF crude product, with ethyl alcohol recrystallization, obtain 5-HMF sterling.By high performance liquid chromatography (HPLC), measure, the yield that in cotton stalk, cellulose conversion is 5-HMF is 51.6%.
Embodiment 2:
Embodiment 1 added to 4: in the material of 1MIBK and water mixed solvent, add 5% (W%) (with cotton stalk powder weighing scale) MCM-41 catalyzer, put into autoclave, temperature rises to 210 ℃, insulation hydrolysis reaction 90min, reaction finishes rear taking-up kettle and carries out coolingly, and then filtration residue obtains cotton stalk hydrolyzed solution, and the water of hydrolyzed solution is with after MIBK extraction, merge with the organic phase of hydrolyzed solution again, after solvent is removed in evaporation, obtain 5-HMF crude product.With HPLC, measuring the yield that in cotton stalk, cellulose conversion is 5-HMF is 43.7%.
Embodiment 3:
(in butt, cellulose 42.3% to change the cotton stalk in embodiment 1 into rice straw, hemicellulose 25.1%, xylogen 4.87%), after the supersound process of 5min, add again the DMSO of 4: 1: water mixed solvent, add 5%MCM-41 catalyzer (W%) (with cotton stalk powder weighing scale), put into autoclave and be warming up to 210 ℃ of setting temperature of reaction, insulation hydrolysis reaction 90min, reaction finishes rear taking-up kettle and carries out coolingly, and then filtration residue obtains straw hydrolyzed solution.After the water of hydrolyzed solution extracts with MIBK, then merge with the organic phase of hydrolyzed solution, after solvent is removed in evaporation, obtain 5-HMF crude product, with HPLC, measuring the yield that in rice straw, cellulose conversion is 5-HMF is 53.9%.
Reference examples 1:
Be to add 3 from the different of embodiment 1: in the material of the mixed solvent of 2MIBK and water, add the H that accounts for reaction system 3%
2sO
4catalyzer (W%), put into autoclave, temperature rises to 230 ℃, insulation hydrolysis reaction 90min, reaction finishes rear taking-up kettle and carries out coolingly, and then filtration residue obtains cotton stalk hydrolyzed solution, and the water of hydrolyzed solution is with after MIBK extraction, merge with the organic phase of hydrolyzed solution again, after solvent is removed in evaporation, obtain 5-HMF crude product.With HPLC, measuring the yield that in cotton stalk, cellulose conversion is 5-HMF is 39.8%.Visible employing sulfuric acid is made catalyzer, and effect will be worse than solid acid catalyst.
Reference examples 2:
(in butt, cellulose 38.2% to change the cotton stalk in embodiment 1 into straw, hemicellulose 20.4%, xylogen 13.4%, ash content 7.9%), then after supersound process, add the pure water solvent of 50 times of weight, add 10%HZSM catalyzer (W%), put into autoclave and be warming up to 210 ℃ of setting temperature of reaction, insulation hydrolysis reaction 90min, reaction finishes rear taking-up kettle and carries out coolingly, and then filtration residue obtains straw hydrolyzed solution.After the water of hydrolyzed solution extracts with MIBK, then merge with the organic phase of hydrolyzed solution, after solvent is removed in evaporation, obtain 5-HMF crude product, with HPLC, measuring the yield that in straw, cellulose conversion is 5-HMF is 40.3%.Visible employing pure water is as solvent, and it is poor that effect is also made solvent than the two-phase system that adopts water-organic solvent.
Following reference examples 3-9 does not all carry out ultrasonication, and not carrying out supersound process is as seen larger on the impact of last yield.
Reference examples 3:
The MIBK of 4: 1 that the cotton stalk of pulverizing is added to 50 times of its weight: water solvent, add 5%HZSM catalyzer (W%, in cotton stalk quality), be warming up to and set 190 ℃ of temperature of reaction, insulation hydrolysis reaction 90min, reaction finishes rear taking-up kettle and carries out coolingly, and then filtration residue obtains cotton stalk hydrolyzed solution.After the water of hydrolyzed solution extracts with MIBK, then merge with the organic phase of hydrolyzed solution, after dissolving is removed in evaporation, obtain 5-HMF crude product, with HPLC, measuring the yield that in cotton stalk, cellulose conversion is 5-HMF is 9.8%.
Reference examples 4:
The pure water solvent that the cotton stalk of pulverizing is added to 50 times of its weight, add 5%MCM-41 catalyzer (W%, in cotton stalk quality), put into autoclave and be warming up to 210 ℃ of setting temperature of reaction, insulation hydrolysis reaction 60min, reaction finishes rear taking-up kettle and carries out coolingly, and then filtration residue obtains cotton stalk hydrolyzed solution.Hydrolyzed solution extracts with MIBK, after solvent is removed in evaporation, obtains 5-HMF crude product, and with HPLC, measuring the yield that in cotton stalk, cellulose conversion is 5-HMF is 9.1%.
Reference examples 5:
By the cotton stalk of pulverizing, the water that adds 1: 1: MIBK makes solvent, solvent adding amount is the weight of 50 times of cotton stalk powders, add 3% (w%) sulfuric acid (in cotton stalk quality), put into autoclave and be warming up to 230 ℃ of setting temperature of reaction, insulation hydrolysis reaction 90min, reaction finishes rear taking-up kettle and carries out coolingly, and then filtration residue obtains cotton stalk hydrolyzed solution.Hydrolyzed solution water, with after MIBK extraction, merges with the organic phase of hydrolyzed solution, after solvent is removed in evaporation, obtains 5-HMF crude product, and with HPLC, measuring the yield that in cotton stalk, cellulose conversion is 5-HMF is 17.3%.
Reference examples 6:
The cotton stalk of pulverizing, the water of 1: 1 that adds 50 times of its weight: MIBK solvent, add 0.5% zinc chloride (W%, in cotton stalk quality), put into autoclave and be warming up to that to set temperature of reaction be 210 ℃, insulation hydrolysis reaction 90min, reaction finishes rear taking-up kettle and carries out coolingly, and then filtration residue obtains cotton stalk hydrolyzed solution.Hydrolyzed solution water, with after MIBK extraction, merges with the organic phase of hydrolyzed solution, after solvent is removed in evaporation, obtains 5-HMF crude product, and with HPLC, measuring the yield that in cotton stalk, cellulose conversion is 5-HMF is 8.0%.
Reference examples 7:
The straw of pulverizing, the water that adds 1: 5: propyl carbinol is made solvent, solvent adding amount is the weight of 70 times of cornstalks, add 0.5% sodium-chlor (W%, in straw quality), put into autoclave and be warming up to 230 ℃ of setting temperature of reaction, insulation hydrolysis reaction 60min, reaction finishes rear taking-up kettle and carries out coolingly, and then filtration residue obtains Corn stalk hydrolysate.The water of hydrolyzed solution is with after many extractions of MIBK, and the organic phase of extraction phase and hydrolyzed solution merges, and after solvent is removed in evaporation, obtains 5-HMF crude product, and with HPLC, measuring the yield that in cornstalk, cellulose conversion is 5-HMF is 6.2%.
Reference examples 8:
The cotton stalk of pulverizing, adds the pure water solvent of 50 times of its weight, and put into autoclave and be warming up to that to set temperature of reaction be 230 ℃, insulation hydrolysis reaction 120min, reaction finishes rear taking-up kettle and carries out coolingly, and then filtration residue obtains cotton stalk hydrolyzed solution.Hydrolyzed solution is with MIBK after repeatedly extracting, and rotary evaporation obtains 5-HMF crude product after removing solvent, and with HPLC, measuring the yield that in cotton stalk, cellulose conversion is 5-HMF is 4.3%.
Reference examples 9:
The rice straw of pulverizing, 11 the water that adds 50 times of its weight: MIBK solvent, put into autoclave and be warming up to that to set temperature of reaction be 230 ℃, insulation hydrolysis reaction 120min, reaction finishes rear taking-up kettle and carries out coolingly, and then filtration residue obtains cotton stalk hydrolyzed solution.Hydrolyzed solution water, with after MIBK extraction, merges with the organic phase of hydrolyzed solution, after solvent is removed in evaporation, obtains 5-HMF crude product, and with HPLC, measuring the yield that in wood chip, cellulose conversion is 5-HMF is 5.4%.
Claims (1)
1. a wood fibre hydrothermal decomposition is prepared the method for 5 hydroxymethyl furfural, it is characterized in that, by cellulose 42.3% in dried butt, hemicellulose 25.1%, the rice straw of xylogen 4.87% is crushed to 40-120 order, by suitable quantity of water, soak, after the supersound process of 5min40kHz, the DMSO that adds again 4:1: water mixed solvent, add 5%MCM-41 catalyzer, with rice straw powder weighing scale, put into autoclave and be warming up to 210 ℃ of setting temperature of reaction, insulation hydrolysis reaction 90min, reaction finishes rear taking-up kettle and carries out cooling, and then filtration residue obtains hydrolyzed solution, after the water of hydrolyzed solution extracts with MIBK, then merge with the organic phase of hydrolyzed solution, after solvent is removed in evaporation, obtain 5-HMF crude product.
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| CN104230860A (en) * | 2014-09-28 | 2014-12-24 | 华南理工大学 | Method for preparing furfural by catalyzing corncobs by two-section process |
| CN105085448B (en) * | 2015-08-21 | 2017-12-29 | 中国科学院上海高等研究院 | A kind of method that 5 hydroxymethylfurfurals are prepared using microalgae as raw material |
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