CN105669421A - Method for preparing levulinic acid and furfural by hydrolyzing biomass - Google Patents
Method for preparing levulinic acid and furfural by hydrolyzing biomass Download PDFInfo
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- CN105669421A CN105669421A CN201610103936.6A CN201610103936A CN105669421A CN 105669421 A CN105669421 A CN 105669421A CN 201610103936 A CN201610103936 A CN 201610103936A CN 105669421 A CN105669421 A CN 105669421A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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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
Abstract
The invention discloses a method for preparing levulinic acid and furfural by hydrolyzing biomass. The method comprises the following steps of firstly, mixing the biomass with a catalyst, introducing water vapor to generate primary hydrolysis, discharging a gaseous phase of the primary hydrolysis and condensing to obtain an aqueous solution containing the furfural; secondly, introducing water vapor into the biomass subjected to primary hydrolysis to perform secondary hydrolysis, and discharging a gaseous phase of the secondary hydrolysis; thirdly, performing temperature and pressure reduction on the gaseous phase subjected to the secondary hydrolysis, enabling the gaseous phase to enter into a reaction kettle filled with the biomass, generating primary hydrolysis, discharging the gaseous phase of the primary hydrolysis, and condensing the gaseous phase to obtain an aqueous solution containing the furfural and the levulinic acid; fourthly, supplementing the catalyst into the reaction still in the third step, introducing water vapor for secondary hydrolysis, and discharging a gaseous phase of the secondary hydrolysis; fifthly, repeating the third step and the fourth step; sixthly, purifying and separating the aqueous solution in the first step from the aqueous solution in the third step to obtain the levulinic acid and the furfural. According to the method disclosed by the invention, the yields of the levulinic acid and the furfural are increased; the yield of the furfural reaches 60 percent or above 60 percent, and the yield of the levulinic acid reaches 50 percent or above 50 percent.
Description
Technical field
The invention belongs to the technical field of chemical industry of biomass, be specifically related to a kind of method that biomass by hydrolyzation prepares levulic acid and furfural.
Background technology
Levulic acid (LevulinicAcid, LA), has another name called 4-oxy pentanoic acid, LA or LA, its outward appearance is white plates or acicular crystal, it is inflammable, low toxicity, have hygroscopicity, does not release carbon dioxide, distill and decompose hardly under normal pressure during heating. Owing to levulic acid molecular structure containing the polyfunctional groups such as carbonyl, carboxyl, methyl and methylene, it is made both to have had the character of carboxylic acid, there is again the character of ketone, there is good chemical reactivity, can be esterified, replace, condensation and neutralization reaction etc., the products such as resin, medicine, pesticide, spice, solvent, coating, ink, rubber, plastic additive, lube oil additive and surfactant can be produced by levulic acid.
Levulic acid can obtain after generating monosaccharide further dehydration and piptonychia acid from cellulose hydrolysis, and cellulose is widely present in the biomass resource of nature, and therefore, how utilizing biomass resource to produce levulic acid becomes study hotspot.
At present, the preparation method of levulic acid can be divided into catalyzed hydrolysis of furfuryl alcohol and hydrolysis of biomass, the two maximum difference being distinctive in that raw material, but furfuryl alcohol is also be hydrolyzed by biomass catalyzing and transfer to obtain, the relatively technique of the two, same with biomass resource for initiation material, catalyzed hydrolysis of furfuryl alcohol needs hydrolysis, dehydration, hydrogenation and hydrolysis four step obtain, and hydrolysis of biomass adds pyrohydrolysis in acid condition and can be prepared by levulic acid with the biomass resource such as cellulose or starch for raw material, the method technique is simple, production cost is low, it it is a kind of method that research is more at present.
Prepare in the research of levulic acid at hydrolysis of biomass, how with furfural dregs, xylose residue, cotton seed hulls, starch etc. for raw material, under low temperature (< 150 DEG C), normal pressure, with mineral acid (HCl or H2SO4) catalysis is hydrolyzed, its deficiency is in that, the response time is longer, side-product is more, yield is relatively low.
Summary of the invention
A kind of method that present invention aim at providing biomass by hydrolyzation to prepare levulic acid and furfural.
Based on object above, the present invention takes techniques below scheme:
A kind of biomass by hydrolyzation prepares the method for levulic acid and furfural, comprises the following steps:
1) after biomass being pulverized, mix in a kettle. by weight 1～1.5:1 with catalyst, pass into 170～180 DEG C, the steam of 0.6～1.0MPa occurs once to be hydrolyzed, when biomass reach 160～180 DEG C with catalyst temperature, the gas phase that discharge is once hydrolyzed, until once hydrolysis terminates, the gas phase that is once hydrolyzed is condensed obtains the aqueous solution containing furfural; Described catalyst is mainly mineral acid, and the response time being once hydrolyzed is 0.8～1h;
2) reactor after there is once hydrolysis to step 1) passes into 210～230 DEG C, the steam of 2.0～2.5MPa carry out secondary hydrolysis, when biomass temperature reaches 200～230 DEG C, the gas phase of discharge secondary hydrolysis, until secondary hydrolysis terminates, the response time of secondary hydrolysis is 1.5～2h;
3) step 2) in secondary hydrolysis gas phase discharge after through being cooled to 170～180 DEG C, being depressurized to 0.6～1.0MPa, enter the next one and have been charged into the reactor of biomass, occur once to be hydrolyzed, when biomass temperature reaches 160～180 DEG C, the gas phase that discharge is once hydrolyzed, until step 2) in secondary hydrolysis terminate, for containing furfural and levulinic aqueous acid after the gas phase that is once hydrolyzed is condensed;
4) to step 3) there is once hydrolysis after reactor in add catalyst, pass into 210～230 DEG C, the steam of 2.0～2.5MPa carry out secondary hydrolysis, when biomass temperature reaches 200～230 DEG C, the gas phase of discharge secondary hydrolysis; The consumption of described catalyst is 1:1～1.5 with the weight ratio of primordial matter in reactor, and described catalyst is mainly mineral acid;
5) step 3 is repeated) and 4);
6) step 3) in aqueous solution add in aqueous slkali and rear and step 1) aqueous solution, purified separation, obtain levulic acid and furfural.
Described mineral acid is dilute sulfuric acid, and dilute sulfuric acid concentration is 3%～5%.
Described 1) and 4) catalyst in possibly together with FeCl3, FeCl3Content in the catalyst is 0.3～0.5%.
Step 1), step 2) and step 4) in the amount ratio of biomass and steam be 1:4.
< 15%, particle diameter is 15-20mm to described biomass moisture content.
The determination method of (a) furfural
According to GB1926.2-1998 " Technical furfural test methods ", adopt the gas chromatograph being furnished with flame ionization ditector, with the diatom great soil group carrier coated Polyethylene Glycol-20M packed column for fixing phase, the specification of packed column: internal diameter is 3mm, the long 4m of pillar, sample size is 0.5ul.
The determination method of (b) levulic acid
Referring to industry standard " in soy sauce the assay method of levulic acid " SB/T10417 2007, adopt the gas chromatograph being furnished with flame ionization ditector, chromatographic column is quartz elastic capillary tube post, fixative is Carbwax-20M, column length 30m, internal diameter 0.25mm, coating thickness 0.5um, adopt external standard method to be analyzed.
The determination method of (c) cellulose, hemicellulose and lignin
Successively analysis sample is carried out neutral detergent, acidic cleaning, 72% sulfuric acid scrubbing, 550 DEG C of ashing, and drying is weighed successively, adopt the content of the cellulose in difference weight method analysis raw material and hydrolytic residue, hemicellulose, lignin.
Compared with prior art, the method have the advantages that
(1) by biomass and catalyst (diluted mineral acid and FeCl3, secondary hydrolysis is formic acid, acetic acid, a small amount of mineral acid and FeCl3) after mixing, pass into 170～180 DEG C, the steam of 0.6～1.0MPa, occur once to be hydrolyzed, biological particles structure is by diluted mineral acid and FeCl3Destroy,But structure of fibrous tissue keeps complete in residue.Carrying out along with hydrolysis, space within biological particles dramatically increases, the dissolving of xylan and diffusibility increase, the distribution of catalyst is more extensive, and, biological particles structural damage causes that in biological particles, specific surface area increases, and thereby increases liquid and vapor interface amasss, enhance the transmission of quality and heat, and be beneficial to separating of steam and furfural.
(2) 210～230 DEG C, 2.0～2.5MPa high-temperature and high-pressure conditions can promote the transfer of electronics in cellulose hydrolysis reaction system, effectively suppress levulic acid to continue the side reactions such as decomposition to occur, it is beneficial to the yield improving levulic acid, and the formic acid contained in product, the organic acid such as acetic acid with steam after heat exchange, the steam reducing to low-temp low-pressure enters next one hydrolysis circulation, thermal source obtains secondary utilization on the one hand, on the other hand, a small amount of mineral acid and byproduct formic acid, acetic acid etc. are as the catalyst of hydrolysis of hemicellulose in next hydrolysis circulation, and in the process, levulic acid decomposes hardly, the gas phase of hydrolysis is discharged, condensed, purification separation.
(3) biomass by hydrolyzation is circulated by said hydrolyzed, takes full advantage of thermal source on the one hand, improves the mass yield of furfural and levulic acid on the other hand, and the mass yield of furfural reaches more than 60%, and the mass yield of levulic acid reaches more than 50%.
Accompanying drawing explanation
Fig. 1 is the structural representation of the corollary apparatus of the present invention.
Detailed description of the invention
Below by specific embodiment, the present invention is described in further details.
Embodiment 1
A kind of biomass by hydrolyzation prepares the method for levulic acid and furfural, comprises the following steps:
1) after 230kg moisture content 11% corn straw (Contents of Main Components is: hemicellulose 25%, cellulose 33%, lignin 16%) being ground into 15mm, be packed in reactor, simultaneously filling 170kg catalyst (concentration be 5% dilute sulfuric acid and the FeCl of concentration 0.5%3), pass into 170 DEG C with the speed of 0.6t/h, the steam of 0.6MPa occurs once to be hydrolyzed, when biomass reach 160 DEG C with catalyst temperature, the gas phase that discharge is once hydrolyzed, until once hydrolysis terminates, the gas phase that is once hydrolyzed is condensed obtains the aqueous solution containing furfural, and the response time being once hydrolyzed is 1h;
2) to step 1) there is once hydrolysis after reactor in the speed of 0.5t/h pass into 210 DEG C, the steam of 2.0MPa carry out secondary hydrolysis, when biomass temperature reaches 200 DEG C, the gas phase of discharge secondary hydrolysis, the response time of secondary hydrolysis is 2h;
3) step 2) in secondary hydrolysis gas phase discharge after be cooled to 170 DEG C through heat exchanger, be depressurized to 0.6MPa, enter the next one through low-pressure steam surge tank and have been charged into the reactor of biomass, occur once to be hydrolyzed, when biomass temperature reaches 160 DEG C, the gas phase that discharge is once hydrolyzed, until step 2) in secondary hydrolysis terminate, for containing furfural and levulinic aqueous acid after the gas phase that is once hydrolyzed is condensed;
4) to step 3) there is once hydrolysis after reactor in add 170kg catalyst (concentration be 5% dilute sulfuric acid and the FeCl of concentration 0.5%3), pass into 210 DEG C, the steam of 2.0MPa carry out secondary hydrolysis, when biomass temperature reaches 200 DEG C, the gas phase of discharge secondary hydrolysis;
5) twice step 3 is repeated) and 4);
6) step 3) in aqueous solution add sodium carbonate liquor be neutralized to pH be 4 and step 1) aqueous solution, be introduced into primary distillation tower, distill out hair aldehyde containing furfural 90-92% (or thick aldehyde), isolate, through rectifying column, the furfural that purity is 98.5%.The levulic acid retained bottom primary distillation tower and the timing of all the other high boiling products enter in dual-effect concentrator, extract after it is carried out vacuum evaporation again, after decompression distillation, obtain levulic acid.
Said hydrolyzed reaction calculates after terminating by analysis, and in raw material, hemicellulose conversion ratio is 100%, cellulose conversion ratio 87.3%, and the yield of furfural is 68.36%, and the yield of levulic acid is 62.45%. The yield of furfural and levulic acid calculates according to below equation.
The yield of furfural=(in hydrolyzed solution total amount × hydrolyzed solution furfural percentage composition)/(in biomass charging (butt) × hydrolyzing biomass hemicellulose percentage composition × 0.72)
The yield of levulic acid=(in hydrolyzed solution total amount × hydrolyzed solution levulic acid percentage composition)/(in biomass straw charging (butt) × hydrolyzing biomass cellulose percentage composition × 0.78)
Embodiment 2
A kind of biomass by hydrolyzation prepares the method for levulic acid and furfural, comprises the following steps:
1) after 280kg moisture content 7% corn cob (Contents of Main Components is: hemicellulose 36%, cellulose 32%, lignin 15%) being ground into 20mm, be packed in reactor, filling 190kg catalyst (concentration be 3% dilute sulfuric acid and the FeCl of concentration 0.3%3), pass into 170 DEG C with the speed of 0.7t/h, the steam of 0.6MPa occurs once to be hydrolyzed, when biomass reach 160 DEG C with catalyst temperature, the gas phase that discharge is once hydrolyzed, until once hydrolysis terminates, the gas phase that is once hydrolyzed is condensed obtains the aqueous solution containing furfural, and the response time being once hydrolyzed is 1h;
2) to step 1) there is once hydrolysis after reactor in the speed of 0.56t/h pass into 210 DEG C, the steam of 2.0MPa carry out secondary hydrolysis, when biomass temperature reaches 200 DEG C, the gas phase of discharge secondary hydrolysis, the response time of secondary hydrolysis is 2h;
3) step 2) in secondary hydrolysis gas phase be cooled to 170 DEG C through heat exchanger, be depressurized to 0.6MPa, enter the next one through low-pressure steam surge tank and have been charged into the reactor of biomass, occur once to be hydrolyzed, when biomass temperature reaches 160 DEG C, the gas phase that discharge is once hydrolyzed, until step 2) in secondary hydrolysis terminate, for containing furfural and levulinic aqueous acid after the gas phase that is once hydrolyzed is condensed;
4) to step 3) there is once hydrolysis after reactor in add 190kg catalyst (concentration be 5% dilute sulfuric acid and the FeCl of concentration 0.5%3), pass into 210 DEG C, the steam of 2.0MPa carry out secondary hydrolysis, when biomass temperature reaches 220 DEG C, the gas phase of discharge secondary hydrolysis;
5) twice step 3 is repeated) and 4);
6) step 3) in aqueous solution add sodium carbonate liquor be neutralized to pH be 4 and step 1) aqueous solution, it is introduced into primary distillation tower, distill out the hair aldehyde (or thick aldehyde) containing furfural 90-92%, isolate, then through rectifying column, the furfural that purity is 98.5%. The levulic acid retained bottom primary distillation tower and the timing of all the other high boiling products enter in dual-effect concentrator, extract after it is carried out vacuum evaporation again, after decompression distillation, obtain levulic acid.
Said hydrolyzed reaction calculates after terminating by analysis, and in raw material, hemicellulose conversion ratio is 100%, cellulose conversion ratio 86.8%, and the yield of furfural is 64.6%, and the yield of levulic acid is 52.8%.
Embodiment 3
A kind of biomass by hydrolyzation prepares the method for levulic acid and furfural, comprises the following steps:
1) after 300kg moisture content 11% wood chip (Contents of Main Components is: hemicellulose 50%, cellulose 30%, lignin 25%) being ground into 10mm, be packed in reactor, simultaneously filling 300kg catalyst (concentration be 5% dilute sulfuric acid and the FeCl of concentration 0.5%3), pass into 180 DEG C with the speed of 0.8t/h, the steam of 1MPa occurs once to be hydrolyzed, when biomass reach 170 DEG C with catalyst temperature, the gas phase that discharge is once hydrolyzed, until once hydrolysis terminates, the gas phase that is once hydrolyzed is condensed obtains the aqueous solution containing furfural, and the response time being once hydrolyzed is 1.1h;
2) to step 1) there is once hydrolysis after reactor in the speed of 0.6t/h pass into 223 DEG C, the steam of 2.5MPa carry out secondary hydrolysis, when biomass temperature reaches 200 DEG C, the gas phase of discharge secondary hydrolysis, the response time of secondary hydrolysis is 2h;
3) step 2) in secondary hydrolysis gas phase discharge after be cooled to 170 DEG C through heat exchanger, be depressurized to 0.6MPa, enter the next one through low-pressure steam surge tank and have been charged into the reactor of biomass, occur once to be hydrolyzed, when biomass temperature reaches 160 DEG C, the gas phase that discharge is once hydrolyzed, until step 2) in secondary hydrolysis terminate, for containing furfural and levulinic aqueous acid after the gas phase that is once hydrolyzed is condensed;
4) to step 3) there is once hydrolysis after reactor in add 300kg catalyst dilute sulfuric acid and the FeCl3 of concentration 0.5% of 5% (concentration be), pass into 223 DEG C, the steam of 2.5MPa carry out secondary hydrolysis, when biomass temperature reaches 200 DEG C, the gas phase of discharge secondary hydrolysis;
5) twice step 3 is repeated) and 4);
6) step 3) in aqueous solution add sodium carbonate liquor be neutralized to pH be 4 and step 1) aqueous solution, be introduced into primary distillation tower, distill out hair aldehyde containing furfural 90-92% (or thick aldehyde), isolate, through rectifying column, the furfural that purity is 98.5%. The levulic acid retained bottom primary distillation tower and the timing of all the other high boiling products enter in dual-effect concentrator, extract after it is carried out vacuum evaporation again, after decompression distillation, obtain levulic acid.
Said hydrolyzed reaction calculates after terminating by analysis, and in raw material, hemicellulose conversion ratio is 100%, cellulose conversion ratio 86.5%, and the yield of furfural is 65.48%, and the yield of levulic acid is 62.45%.
Providing below one can corollary apparatus corresponding with above-described embodiment 1-3, as shown in Figure 1, including 4 reactors 15, each reactor top is provided with charging aperture 1, catalyst inlet 2 and gas outlet 3, bottom is provided with waste residue outlet 4 and air inlet 5, described catalyst inlet 2 is connected to the catalyst storage tank 6 of the lower section being positioned at reactor, pipeline between catalyst storage tank 6 and catalyst inlet 2 is provided with feed pump 7, the pipeline of gas outlet 3 is connected to the first gas phase pipeline 8-1 and the second gas phase pipeline 8-2, the port of export of the second gas phase pipeline 8-2 is connected with the second heat exchanger 9-2 in turn and is provided with the acid-base neutralization tank 10 of discharging opening, the discharging opening of acid-base neutralization tank 10 is connected to purification separation device 11, acid-base neutralization tank 10 is also associated with alkali liquor storage tank 16, the pipeline of air inlet 5 is connected to the first steam pipework 12-1 and the second steam pipework 12-2, the port of export of described first gas phase pipeline 8-1 is connected with First Heat Exchanger 9-1 and low-pressure steam surge tank 13 in turn, the gas outlet on described low-pressure steam surge tank 13 top connects with the second steam pipework 12-2, described first gas phase pipeline 8-1, second gas phase pipeline 8-2, first steam pipework 12-1 and the second steam pipework 12-2 is provided with stop valve 14.
Claims (5)
1. the method that a biomass by hydrolyzation prepares levulic acid and furfural, it is characterised in that comprise the following steps:
1) after biomass being pulverized, mix in a kettle. by weight 1～1.5:1 with catalyst, pass into 170～180 DEG C, the steam of 0.6～1.0MPa occurs once to be hydrolyzed, when biomass reach 160～180 DEG C with catalyst temperature, the gas phase that discharge is once hydrolyzed, until once hydrolysis terminates, the gas phase that is once hydrolyzed is condensed obtains the aqueous solution containing furfural;Described catalyst is mainly mineral acid, and the response time being once hydrolyzed is 0.8～1h;
2) reactor after there is once hydrolysis to step 1) passes into 210～230 DEG C, the steam of 2.0～2.5MPa carry out secondary hydrolysis, when biomass temperature reaches 200～230 DEG C, the gas phase of discharge secondary hydrolysis, until secondary hydrolysis terminates, the response time of secondary hydrolysis is 1.5～2h;
3) step 2) in secondary hydrolysis gas phase discharge after through being cooled to 170～180 DEG C, being depressurized to 0.6～1.0MPa, enter the next one and have been charged into the reactor of biomass, occur once to be hydrolyzed, when biomass temperature reaches 160～180 DEG C, the gas phase that discharge is once hydrolyzed, until step 2) in secondary hydrolysis terminate, for containing furfural and levulinic aqueous acid after the gas phase that is once hydrolyzed is condensed;
4) to step 3) there is once hydrolysis after reactor in add catalyst, pass into 210～230 DEG C, the steam of 2.0～2.5MPa carry out secondary hydrolysis, when biomass temperature reaches 200～230 DEG C, the gas phase of discharge secondary hydrolysis; The consumption of described catalyst is 1:1～1.5 with the weight ratio of primordial matter in reactor, and catalyst is mainly mineral acid;
5) step 3 is repeated) and 4);
6) step 3) in aqueous solution add in aqueous slkali and rear and step 1) aqueous solution, purified separation, obtain levulic acid and furfural.
2. the method that biomass by hydrolyzation according to claim 1 prepares levulic acid and furfural, it is characterised in that described mineral acid is dilute sulfuric acid, dilute sulfuric acid concentration is 3%～5%.
3. the method that biomass by hydrolyzation according to claim 2 prepares levulic acid and furfural, it is characterised in that possibly together with FeCl in the catalyst of described step 1) and step 4)3, FeCl3Content in the catalyst is 0.3～0.5%.
4. the method that the biomass by hydrolyzation according to claim 1,2 or 3 prepares levulic acid and furfural, it is characterised in that step 1), step 2) and step 4) in the amount ratio of biomass and steam be 1:4.
5. the method that biomass by hydrolyzation according to claim 4 prepares levulic acid and furfural, it is characterised in that < 15%, particle diameter is 15-20mm to described biomass moisture content.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017170093A1 (en) * | 2016-03-30 | 2017-10-05 | 王子ホールディングス株式会社 | Furfural composition and method for producing furfural composition |
| CN107540642A (en) * | 2017-10-12 | 2018-01-05 | 河南省科学院能源研究所有限公司 | A kind of method that furfural and levulic acid are prepared using biomass clean hydrolysis |
| CN107759544A (en) * | 2017-10-11 | 2018-03-06 | 肥城金威机械有限公司 | Method for hydrolysis, device and its application for furfural |
| CN107973709A (en) * | 2017-11-23 | 2018-05-01 | 莫祖勇 | A kind of biomass-based method for preparing methyl ester levulinate |
| CN108003003A (en) * | 2017-12-06 | 2018-05-08 | 东莞理工学院 | A kind of method for preparing high concentration levulic acid |
| CN108912072A (en) * | 2018-10-08 | 2018-11-30 | 肥城金威机械有限公司 | Preparation facilities and method and the application of furfural are produced using straw |
| CN111440134A (en) * | 2020-04-23 | 2020-07-24 | 华东理工大学 | Method and device for coproduction of furfural and levulinic acid by biomass fractional hydrolysis |
| CN115245842A (en) * | 2022-08-12 | 2022-10-28 | 中国矿业大学 | Biological guide type multi-component three-way acid catalyst and application thereof |
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| CN104311411A (en) * | 2014-09-15 | 2015-01-28 | 淮阴师范学院 | Method for preparing levulinic acid by multistage acid hydrolysis |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017170093A1 (en) * | 2016-03-30 | 2017-10-05 | 王子ホールディングス株式会社 | Furfural composition and method for producing furfural composition |
| CN107759544A (en) * | 2017-10-11 | 2018-03-06 | 肥城金威机械有限公司 | Method for hydrolysis, device and its application for furfural |
| CN107540642A (en) * | 2017-10-12 | 2018-01-05 | 河南省科学院能源研究所有限公司 | A kind of method that furfural and levulic acid are prepared using biomass clean hydrolysis |
| CN107540642B (en) * | 2017-10-12 | 2020-01-14 | 河南省科学院能源研究所有限公司 | Method for preparing furfural and levulinic acid by utilizing clean hydrolysis of biomass |
| CN107973709A (en) * | 2017-11-23 | 2018-05-01 | 莫祖勇 | A kind of biomass-based method for preparing methyl ester levulinate |
| CN108003003A (en) * | 2017-12-06 | 2018-05-08 | 东莞理工学院 | A kind of method for preparing high concentration levulic acid |
| CN108912072A (en) * | 2018-10-08 | 2018-11-30 | 肥城金威机械有限公司 | Preparation facilities and method and the application of furfural are produced using straw |
| CN111440134A (en) * | 2020-04-23 | 2020-07-24 | 华东理工大学 | Method and device for coproduction of furfural and levulinic acid by biomass fractional hydrolysis |
| CN111440134B (en) * | 2020-04-23 | 2024-03-29 | 华东理工大学 | Method and device for coproducing furfural and levulinic acid through biomass fractional hydrolysis |
| CN115245842A (en) * | 2022-08-12 | 2022-10-28 | 中国矿业大学 | Biological guide type multi-component three-way acid catalyst and application thereof |
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