CN104402712A - Method for preparing levulinic acid ester through variable temperature method - Google Patents

Method for preparing levulinic acid ester through variable temperature method Download PDF

Info

Publication number
CN104402712A
CN104402712A CN201410566843.8A CN201410566843A CN104402712A CN 104402712 A CN104402712 A CN 104402712A CN 201410566843 A CN201410566843 A CN 201410566843A CN 104402712 A CN104402712 A CN 104402712A
Authority
CN
China
Prior art keywords
temperature
levulinate
acid
reaction
acid ester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410566843.8A
Other languages
Chinese (zh)
Other versions
CN104402712B (en
Inventor
袁振宏
谭雪松
庄新姝
亓伟
余强
王琼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangzhou Institute of Energy Conversion of CAS
Original Assignee
Guangzhou Institute of Energy Conversion of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangzhou Institute of Energy Conversion of CAS filed Critical Guangzhou Institute of Energy Conversion of CAS
Priority to CN201410566843.8A priority Critical patent/CN104402712B/en
Publication of CN104402712A publication Critical patent/CN104402712A/en
Application granted granted Critical
Publication of CN104402712B publication Critical patent/CN104402712B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/08—Fractionation of cellulose, e.g. separation of cellulose crystallites
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Biotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a way using variable temperature continuous alcoholysis, and with a cellulose substance as a raw material, in a short-chain alcohol medium, and in the presence of an acid catalyst, a method for preparing levulinic acid ester through a variable temperature method is provided. The method includes the specific steps: mixing the cellulose substance subjected to decrystallization treatment, the short-chain alcohol and the acid catalyst, in an inert gas atmosphere, carrying out a high-temperature reaction for a period of time, cooling, continuing reaction for a period of time at the low temperature, cooling, and thus obtaining levulinic acid ester. Through the decrystallization treatment, the alcoholysis reaction activity of the cellulose substance is improved; through adopting of the variable temperature continuous alcoholysis way, in the high-temperature reaction stage, the yield of an intermediate product alkyl glucoside is selectively increased, in the low temperature reaction stage, generation of side reactions are suppressed, the conversion selectivity of alkyl glucoside to levulinic acid ester is increased, and thus the yield of levulinic acid ester is increased on the whole. The method has the advantages of rich raw material sources, simple craft process, low production cost, and high yield of levulinic acid ester.

Description

A kind of temperature-switching method prepares the method for levulinate
Technical field
The present invention relates to the chemical industrial field of biomass, be specifically related to a kind of mode adopting alternating temperature continuous alcoholysis, take cellulose substances as raw material, after decrystallization process, in short-chain alcohols medium, under acid catalyst exists, the method for levulinate is prepared in alternating temperature reaction.
Background technology
Carbonyl, ester group and α hydrogen is comprised in levulinic acid ester molecule, there is fine reactive behavior, can carry out being oxidized, reduce, replace, be polymerized, the various reaction such as addition, be a kind of Important Platform compound in industries such as coating, spices, food and medicines with wide application prospect.The short-chain aliphatic ester of levulinic acid, because its character and biofuel are very similar, therefore can as a kind of potential source biomolecule fuel or fuel dope.
At present, the production method of levulinate mainly contains four approach: levulinic acid esterification method, furfuryl alcohol alcoholysis method, 5-chloromethyl furfural alcoholysis method and biomass alcohol solution.Levulinic acid esterification method reaction conditions is gentle, and yield is higher, but because of raw material levulinic acid expensive, cause this method to produce levulinate high expensive.Furfuryl alcohol alcoholysis method obtains furfuryl alcohol by hydrogenation of furfural, and then furfuryl alcohol alcoholysis obtains ethyl levulinate, this method polystep reaction, and relate to high-pressure hydrogenation, thus complex process, equipment requirements is high, limits the development in this path.The participation of concentrated hydrochloric acid is needed in the preparation process of the raw material 5-chloromethyl furfural of 5-chloromethyl furfural alcoholysis method, serious to equipment corrosion, meanwhile, halogen needs to remove in generation product levulinate, add material consumption and environmental stress, this all hinders the large-scale application in this path.Biomass alcohol solution, raw material sources are extensive, and technique is simple, is produce the path that levulinate comparatively has development prospect at present.
The reaction process that levulinate is prepared in the alcoholysis of cellulose biomass direct acid catalysis is as follows:
This reaction process can under acid catalyst effect, and Mierocrystalline cellulose carries out mix common heat condition with alcohol medium under.First, Mierocrystalline cellulose alcoholysis generates alkyl-glucoside; Alkyl-glucoside dewaters further and generates 5-alkoxymethylfurfural; And then alcoholysis generates levulinate further.This path for transformation need experience multistep pilot process, and simultaneously each step is attended by side reaction and occurs, and causes by product more, levulinate yield is lower wait not enough.
Summary of the invention
The invention provides a kind of mode adopting alternating temperature continuous alcoholysis, take cellulose substances as raw material, and after decrystallization process, in short-chain alcohols medium, under acid catalyst exists, the method for levulinate is prepared in temperature-switching method reaction.Present method abundant raw material source, technological process is simple, and the molar yield of levulinate can reach 67%.
Temperature-switching method provided by the present invention prepares the method for levulinate, and concrete steps are:
By through the mixing of the cellulose substances of decrystallization process, short chain alcohol and acid catalyst, in atmosphere of inert gases, after pyroreaction for some time, cooling continued in low-temp reaction for some time, and cooling, obtains levulinate.
The treating processes that decrystallization is treated to ball-milling processing, phosphoric acid solvent treatment, chlorination 1-butyl-3-Methylimidazole ([Bmim] Cl) ionic liquid process etc. can reduce cellulose crystallity.Pyroreaction temperature is 160 ~ 240 DEG C, and the reaction times is 0.5 ~ 2h; Low-temp reaction temperature is 120 ~ 180 DEG C, and the reaction times is 0.5 ~ 8h.
Cellulose substances comprises the biomass containing cellulosic component such as Microcrystalline Cellulose, bagasse, Eucalyptus bits.
Short chain alcohol is selected from methyl alcohol, ethanol, propyl alcohol or butanols.
Acid catalyst is mineral acid or solid acid.Mineral acid is selected from sulfuric acid, phosphoric acid, nitric acid or hydrochloric acid.Solid acid is selected from heteropolyacid (as phospho-wolframic acid H 3pW 12o 40), acidic cs salts of heteropolyacid is (as phospho-wolframic acid cesium salt Cs xh 3-xpW 12o 40), ZSM-5, HY type molecular sieve, Amberlyst-15 or sulfonation carbon.
Preferably, the mass ratio through the cellulose substances of decrystallization process, short chain alcohol and acid catalyst is 1:10 ~ 80:0.1 ~ 2.The pressure of atmosphere of inert gases is 0.5 ~ 5MPa.
The present invention take cellulose substances as raw material, and use acid catalyst to carry out catalyzed alcoholysis reaction to Mierocrystalline cellulose and directly prepare levulinate, abundant raw material source, technological process is simple, saves production cost; The present invention, by decrystallization process, improves cellulose substances alcoholysis reaction active, increases the conversion of cellulose substances raw material; The present invention adopts the mode of alternating temperature continuous alcoholysis, in the pyroreaction stage, selectivity improves the yield of intermediate product alkyl-glucoside, in the low-temp reaction stage, side reaction is suppressed to occur, improve the selectivity that alkyl-glucoside transforms to levulinate, and then improve levulinate yield on the whole.
Embodiment
Method in following embodiment, if no special instructions, is ordinary method.
Embodiment 1:
1g is placed in autoclave through the Microcrystalline Cellulose of phosphoric acid solvent decrystallization process, 10g methyl alcohol, the mixing of 0.1g sulfuric acid, in 4MPa nitrogen atmosphere, at 200 DEG C after stirring reaction 1h, be cooled to 120 DEG C of reaction 8h, cooling leaves standstill, after release, liquid product gas-chromatography coupling mass spectrograph carrys out quantitative and qualitative analysis detection, and the molar yield of methyl ester levulinate is 62%.
Embodiment 2:
Table 1 shows 1g and is placed in autoclave through the cellulose substances of decrystallization process, 20g methyl alcohol, the mixing of 0.1g sulfuric acid, in 4MPa nitrogen atmosphere, and the yield of methyl ester levulinate under the different alternating temperature reaction conditions of different cellulose family raw material.
The yield of methyl ester levulinate under the different alternating temperature reaction conditions of the different cellulose family raw material of table 1
Embodiment 3:
By Microcrystalline Cellulose, 80g butanols, the 0.5g phospho-wolframic acid (H of 1g through the process of phosphoric acid solvent decrystallization 3pW 12o 40) mixing be placed in autoclave, in 0.5MPa argon atmosphere, at 200 DEG C after stirring reaction 1h, be cooled to 140 DEG C of reaction 4h, cooling leaves standstill, and after release, liquid product gas-chromatography coupling mass spectrograph carrys out quantitative and qualitative analysis detection, and the molar yield of Butyl acetylpropanoate is 42%.
Embodiment 4:
By Microcrystalline Cellulose, 20g ethanol, the 0.5g phospho-wolframic acid cesium salt (Cs of 1g through the process of phosphoric acid solvent decrystallization xh 3-xpW 12o 40) mixing be placed in autoclave, in 5MPa nitrogen atmosphere, at 180 DEG C after stirring reaction 1h, be cooled to 140 DEG C of reaction 4h, cooling leaves standstill, and after release, liquid product gas-chromatography coupling mass spectrograph carrys out quantitative and qualitative analysis detection, and the molar yield of ethyl levulinate is 54%.
Embodiment 5:
By Microcrystalline Cellulose, 80g butanols, the 0.5g phospho-molybdic acid (H of 1g through the process of phosphoric acid solvent decrystallization 3pMoO 40) mixing be placed in autoclave, in 0.5MPa argon atmosphere, at 200 DEG C after stirring reaction 1h, be cooled to 140 DEG C of reaction 2h, cooling leaves standstill, and after release, liquid product gas-chromatography coupling mass spectrograph carrys out quantitative and qualitative analysis detection, and the molar yield of Butyl acetylpropanoate is 40%.
Embodiment 6:
1g is placed in autoclave through the Microcrystalline Cellulose of phosphoric acid solvent decrystallization process, 40g propyl alcohol, 2g ZSM-5 mixing, in 0.5Mpa helium atmosphere, at 160 DEG C after stirring reaction 2h, be cooled to 140 DEG C of reaction 4h, cooling leaves standstill, after release, liquid product gas-chromatography coupling mass spectrograph carrys out quantitative and qualitative analysis detection, and the molar yield of levulinic acid propyl ester is 37%.
Embodiment 7:
1g is placed in autoclave through the Microcrystalline Cellulose of phosphoric acid solvent decrystallization process, 20g ethanol, the mixing of 0.5g sulfonation carbon, in 4MPa nitrogen atmosphere, at 180 DEG C after stirring reaction 2h, be cooled to 160 DEG C of reaction 1h, cooling leaves standstill, after release, liquid product gas-chromatography coupling mass spectrograph carrys out quantitative and qualitative analysis detection, and the molar yield of ethyl levulinate is 67%.
Embodiment 8:
1g is placed in autoclave through the Microcrystalline Cellulose of phosphoric acid solvent decrystallization process, 20g ethanol, the mixing of 0.5g HY type molecular sieve, in 4MPa nitrogen atmosphere, at 180 DEG C after stirring reaction 2h, be cooled to 160 DEG C of reaction 1h, cooling leaves standstill, after release, liquid product gas-chromatography coupling mass spectrograph carrys out quantitative and qualitative analysis detection, and the molar yield of ethyl levulinate is 56%.
Embodiment 9:
1g is placed in autoclave through the Microcrystalline Cellulose of phosphoric acid solvent decrystallization process, 20g ethanol, 0.5g Amberlyst-15 mixing, in 4MPa nitrogen atmosphere, at 160 DEG C after stirring reaction 2h, be cooled to 120 DEG C of reaction 6h, cooling leaves standstill, after release, liquid product gas-chromatography coupling mass spectrograph carrys out quantitative and qualitative analysis detection, and the molar yield of ethyl levulinate is 42%.
Embodiment 10:
1g is placed in autoclave through the Microcrystalline Cellulose of ball milling decrystallization process, 20g ethanol, the mixing of 0.5g phosphoric acid, in 4MPa nitrogen atmosphere, at 180 DEG C after stirring reaction 2h, be cooled to 160 DEG C of reaction 1h, cooling leaves standstill, after release, liquid product gas-chromatography coupling mass spectrograph carrys out quantitative and qualitative analysis detection, and the molar yield of ethyl levulinate is 51%.

Claims (6)

1. a temperature-switching method prepares the method for levulinate, it is characterized in that, concrete steps are: by through the mixing of the cellulose substances of decrystallization process, short chain alcohol and acid catalyst, in atmosphere of inert gases, after pyroreaction for some time, cooling continued in low-temp reaction for some time, and cooling, obtains levulinate; Described decrystallization is treated to a kind for the treatment of processes reducing cellulose crystallity, is selected from ball-milling processing, phosphoric acid solvent treatment or the process of chlorination 1-butyl-3-Methylimidazole ionic liquid; Described pyroreaction temperature is 160 ~ 240 DEG C, and the reaction times is 0.5 ~ 2h; Described low-temp reaction temperature is 120 ~ 180 DEG C, and the reaction times is 0.5 ~ 8h.
2. temperature-switching method as claimed in claim 1 prepares the method for levulinate, and it is characterized in that, described cellulose substances is the biomass containing cellulosic component, is selected from Microcrystalline Cellulose, bagasse or Eucalyptus bits.
3. temperature-switching method as claimed in claim 1 prepares the method for levulinate, and it is characterized in that, described short chain alcohol is selected from methyl alcohol, ethanol, propyl alcohol or butanols.
4. temperature-switching method as claimed in claim 1 prepares the method for levulinate, and it is characterized in that, described acid catalyst is mineral acid or solid acid; Described mineral acid is selected from sulfuric acid, phosphoric acid, nitric acid or hydrochloric acid; Described solid acid is selected from heteropolyacid, acidic cs salts of heteropolyacid, ZSM-5, HY type molecular sieve, Amberlyst-15 or sulfonation carbon.
5. temperature-switching method as claimed in claim 1 prepares the method for levulinate, and it is characterized in that, the mass ratio of the described cellulose substances through decrystallization process, short chain alcohol and acid catalyst is 1:10 ~ 80:0.1 ~ 2.
6. temperature-switching method as claimed in claim 1 prepares the method for levulinate, and it is characterized in that, the pressure of described atmosphere of inert gases is 0.5 ~ 5MPa.
CN201410566843.8A 2014-10-22 2014-10-22 A kind of temperature-switching method prepares the method for levulinate Active CN104402712B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410566843.8A CN104402712B (en) 2014-10-22 2014-10-22 A kind of temperature-switching method prepares the method for levulinate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410566843.8A CN104402712B (en) 2014-10-22 2014-10-22 A kind of temperature-switching method prepares the method for levulinate

Publications (2)

Publication Number Publication Date
CN104402712A true CN104402712A (en) 2015-03-11
CN104402712B CN104402712B (en) 2016-07-06

Family

ID=52640395

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410566843.8A Active CN104402712B (en) 2014-10-22 2014-10-22 A kind of temperature-switching method prepares the method for levulinate

Country Status (1)

Country Link
CN (1) CN104402712B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105254768A (en) * 2015-11-12 2016-01-20 江苏瑞晨化学有限公司 Preparation method of low-propionyl-content cellulose acetate propionate mixed ester
CN105859545A (en) * 2016-04-07 2016-08-17 中国科学技术大学 Preparation method of furfural and levulinic acid
CN106349045A (en) * 2016-07-28 2017-01-25 东莞理工学院 Method of preparing levulinic acid and sulfonated carbon catalyst through one-pot process
CN111171161A (en) * 2020-02-19 2020-05-19 江苏瑞佳新材料有限公司 Cellulose acetate butyrate and preparation method thereof
CN112473736A (en) * 2020-12-04 2021-03-12 北华大学 Novel supported polyacid catalyst and application thereof in preparation of levulinate
CN112705247A (en) * 2019-10-24 2021-04-27 中国石油化工股份有限公司 Solid acid catalyst and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101182686A (en) * 2007-12-07 2008-05-21 华南理工大学 Decrystallizing method of cellulose in ion liquid
US20110003341A1 (en) * 2007-12-27 2011-01-06 Kao Corporation Process for producing saccharide
CN102112432A (en) * 2008-06-26 2011-06-29 波利玛利欧洲股份公司 Process for production of esters of levulinic acid from biomasses
CN103724201A (en) * 2014-01-17 2014-04-16 郑州大学 Method for preparing ethyl levulinate by catalyzing biomass sugar to be directly alcoholyzed

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101182686A (en) * 2007-12-07 2008-05-21 华南理工大学 Decrystallizing method of cellulose in ion liquid
US20110003341A1 (en) * 2007-12-27 2011-01-06 Kao Corporation Process for producing saccharide
CN102112432A (en) * 2008-06-26 2011-06-29 波利玛利欧洲股份公司 Process for production of esters of levulinic acid from biomasses
CN103724201A (en) * 2014-01-17 2014-04-16 郑州大学 Method for preparing ethyl levulinate by catalyzing biomass sugar to be directly alcoholyzed

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
曾珊珊等: "固体酸SO4-/TiO2催化葡萄糖制备乙酰丙酸甲酯", 《现代食品科技》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105254768A (en) * 2015-11-12 2016-01-20 江苏瑞晨化学有限公司 Preparation method of low-propionyl-content cellulose acetate propionate mixed ester
CN105859545A (en) * 2016-04-07 2016-08-17 中国科学技术大学 Preparation method of furfural and levulinic acid
CN106349045A (en) * 2016-07-28 2017-01-25 东莞理工学院 Method of preparing levulinic acid and sulfonated carbon catalyst through one-pot process
CN106349045B (en) * 2016-07-28 2018-06-29 东莞理工学院 A kind of method that one kettle way prepares levulic acid and sulfonation C catalyst
CN112705247A (en) * 2019-10-24 2021-04-27 中国石油化工股份有限公司 Solid acid catalyst and preparation method and application thereof
CN112705247B (en) * 2019-10-24 2022-12-09 中国石油化工股份有限公司 Solid acid catalyst and preparation method and application thereof
CN111171161A (en) * 2020-02-19 2020-05-19 江苏瑞佳新材料有限公司 Cellulose acetate butyrate and preparation method thereof
CN111171161B (en) * 2020-02-19 2020-09-11 江苏瑞佳新材料有限公司 Cellulose acetate butyrate and preparation method thereof
CN112473736A (en) * 2020-12-04 2021-03-12 北华大学 Novel supported polyacid catalyst and application thereof in preparation of levulinate
CN112473736B (en) * 2020-12-04 2023-07-07 北华大学 Supported polyacid catalyst and application thereof in preparation of levulinate

Also Published As

Publication number Publication date
CN104402712B (en) 2016-07-06

Similar Documents

Publication Publication Date Title
CN104402712B (en) A kind of temperature-switching method prepares the method for levulinate
CN103724201B (en) The method of levulinate is prepared in the direct alcoholysis of a kind of catalysis biomass sugar
Sun et al. Lysine functional heteropolyacid nanospheres as bifunctional acid–base catalysts for cascade conversion of glucose to levulinic acid
CN103012334A (en) Method for preparing gamma-valerolactone with high selectivity under mild condition
CN104177319A (en) Method for preparing 2,5-furyldiformate
Bernardo et al. HReO4 as highly efficient and selective catalyst for the conversion of carbohydrates into value added chemicals
CN107417485B (en) Method for directly preparing exo-tetrahydrodicyclopentadiene from dicyclopentadiene
CN109985626B (en) Method for preparing ethyl furfuryl ether by furfural liquid phase hydrogenation, catalyst and preparation method of catalyst
Liu et al. Glucose dehydration to 5-hydroxymethylfurfural in ionic liquid over Cr 3+-modified ion exchange resin
CN104725229A (en) Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate
CN103275096A (en) Method for preparing isosorbide based on cellulose
CN105566258A (en) Method of preparing gamma-valerolactone from acetyl ethyl propanoate
CN105669456A (en) Method for preparing valerate from levulinic acid
EP3088381B1 (en) Method for preparing polyoxymethylene dimethyl ether carbonyl compound and methyl methoxyacetate
CN101412661B (en) Solid-state cardanol and preparation thereof
CN107903224A (en) Acidic catalyst and hydrogenation catalyst concerted catalysis carbohydrate one kettle way prepare γ valerolactones
CN104788408B (en) A kind of method that γ valerolactones are produced by hemicellulose
CN105924414B (en) A kind of method that 5 hydroxymethyl furfural is produced by carbohydrate
CN105884616B (en) A kind of technique that furfural two step method continuously prepares methyl ester levulinate
CN102173977B (en) Cu/Al2O3 catalyst and preparation method thereof as well as method for catalyzing hydrolysis of glycerol
CN103387495A (en) Method for the continuous production of carboxylic acid esters
CN102153446A (en) Cu/MgO catalyst, preparation method thereof and method for catalyzing glycerin hydrogenolysis
CN103691479A (en) Preparation method and application of composite catalyst
CN105254601A (en) Method for preparing 5-HMF(hydroxymethylfurfural) from glucose
CN104402723B (en) A kind of alkyl-glucoside prepares the method for levulinate and manthanoate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant