CN117384115A - Preparation method of biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative ester thereof - Google Patents
Preparation method of biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative ester thereof Download PDFInfo
- Publication number
- CN117384115A CN117384115A CN202311160574.0A CN202311160574A CN117384115A CN 117384115 A CN117384115 A CN 117384115A CN 202311160574 A CN202311160574 A CN 202311160574A CN 117384115 A CN117384115 A CN 117384115A
- Authority
- CN
- China
- Prior art keywords
- bistetrahydrofuran
- dicarboxylic acid
- derivative
- biomass
- esters
- 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.)
- Pending
Links
- 150000002148 esters Chemical class 0.000 title claims abstract description 41
- 239000002028 Biomass Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000004065 semiconductor Substances 0.000 claims abstract description 15
- 238000005859 coupling reaction Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 5
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical group [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 5
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 5
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 4
- 238000007146 photocatalysis Methods 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000011 cadmium carbonate Inorganic materials 0.000 claims description 2
- GKDXQAKPHKQZSC-UHFFFAOYSA-L cadmium(2+);carbonate Chemical compound [Cd+2].[O-]C([O-])=O GKDXQAKPHKQZSC-UHFFFAOYSA-L 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 238000006356 dehydrogenation reaction Methods 0.000 abstract 1
- 238000006479 redox reaction Methods 0.000 abstract 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 10
- 238000004451 qualitative analysis Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- -1 etc.) Chemical compound 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000006709 oxidative esterification reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
Classifications
-
- 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
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative esters thereof. The method utilizes a semiconductor photocatalyst to dimerize 2-tetrahydrofurfuryl acid and derivative esters thereof into 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative esters thereof through a C-C bond dehydrogenation coupling reaction. The invention has high coupling efficiency and high product yield; the ultraviolet light or visible light is used as driving force to carry out oxidation-reduction reaction, so that the method is economical and environment-friendly and has good application prospect.
Description
Technical Field
The invention belongs to the field of chemistry, and particularly relates to a preparation method of biomass-based polyester monomer (2, 2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative esters thereof).
Background
Biomass comprises cellulose, hemicellulose, lignin and the like, is the largest renewable carbon resource on the earth, and the consumption of fossil resources can be effectively reduced by taking biomass as a raw material to prepare renewable polymers. The five-carbon sugar obtained after hemicellulose depolymerization can be further dehydrated to generate furfural. Due to the simpler preparation method, the furfural is produced in large scale from 1923, and the current worldwide furfural yield is about 25 ten thousand tons per year.
The 2-tetrahydrofurfuryl acid and the derivative ester thereof can be prepared from furfural through oxidative esterification and hydrogenation reaction, and are one of important derivatives of the furfural. The object of the present invention was to develop a process for converting 2-tetrahydrofurfuryl acid and its derivatives into 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and its derivatives. The 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and its derivative esters can be used directly as polyester monomers. The method adopts a photocatalysis method, under the irradiation of ultraviolet light or visible light, a semiconductor catalyst is utilized to carry out C-C coupling reaction, and 2-tetrahydrofurfuryl acid and derivative esters thereof are converted into 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative esters thereof. The method has high coupling efficiency, high product yield and good application prospect.
Disclosure of Invention
The present invention aims to provide a method for preparing biomass-based polyester monomer (2, 2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative esters thereof). The invention also provides a catalyst for converting 2-tetrahydrofurfuryl acid and derivative esters thereof into 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative esters thereof.
The technical scheme of the invention is as follows:
the preparation method of biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative esters thereof adopts a photocatalysis method, and under the irradiation of ultraviolet light or visible light, a semiconductor catalyst is utilized to carry out C-C coupling reaction, so that 2-tetrahydrofurfuryl acid and derivative esters thereof are converted into 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative esters thereof.
The structural formula of the 2-tetrahydrofurfuryl acid and the derivative ester thereof is The structural formula of the product 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and the derivative ester thereof is +.>
The wavelength range of the ultraviolet light or visible light is 300-800nm.
The semiconductor catalyst comprises titanium (titanium dioxide, excessive noble metal or noble metal supported titanium dioxide Cu/TiO) 2 、Au/TiO 2 、Ru/TiO 2 Etc.), bismuth (bismuth oxide, bismuth trioxide, bismuth tungstate, transition metal or noble metal supported bismuth tungstate, etc.), cadmium (cadmium oxide, cadmium sulfide, cadmium carbonate, and transition metal or noble metalAnd belongs to loaded cadmium oxide, cadmium sulfide and the like).
The reaction temperature of the system is 10-30 ℃; the reaction time is 0.5-48h; the mass ratio of the semiconductor catalyst to the 2-tetrahydrofurfuryl acid and the derivative ester thereof is as follows: 0.1-10wt%.
Adding or not adding a solvent in the reaction, wherein the solvent is one or more than two of toluene, o-xylene, acetonitrile, dichloromethane and dimethyl sulfoxide; stirring is carried out during the reaction.
The invention has the beneficial effects that:
the invention converts biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative esters thereof into 2,2 '-bistetrahydrofuran-2, 2' -)
Dicarboxylic acids and their derived esters, the products can be used directly as polyester monomers. The invention adopts a photocatalysis method, uses semiconductor materials such as titanium dioxide and the like as a photocatalyst, and is environment-friendly. The catalyst system of the invention is simple and efficient, and can convert 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative esters thereof into 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative esters thereof with high selectivity in a short time by using a small amount of catalyst.
Detailed Description
The invention is illustrated by the following specific examples, but the practice of the invention is not limited to these examples:
examples 1 to 14: 0.5mmol of methyl 2-tetrahydrofurfuryl acid, 5mg of titanium dioxide and 2mL of solvent (no solvent is added in example 1) are added to a 10mL photoreactor, the reactor is closed, the reaction temperature is room temperature and the reaction is carried out for a certain time under irradiation of 365nm light. The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, the quantitative analysis is realized by gas chromatography, and the results are shown in table 1.
TABLE 1 optimization of reaction conditions
As a result of analysis of the results in Table 1, it was found that acetonitrile was a preferred solvent for converting methyl 2-tetrahydrofurfuryl acid into dimethyl 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylate by titanium dioxide under the conditions of 40W power lamp reaction, the conversion rate of methyl 12h, 2-tetrahydrofurfuryl acid was 96%, and the selectivity of dimethyl 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylate was 97%.
Examples 15-25 0.5mmol of methyl 2-tetrahydrofurfuryl acid, a certain amount of catalyst and 2mL of acetonitrile are added into a 10mL photo-reactor, the reactor is closed, the reaction temperature is room temperature, and the reaction is carried out for a certain time under the condition of illumination. The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, the quantitative analysis is realized by gas chromatography, and the results are shown in Table 2.
TABLE 2 influence of different catalysts on catalytic reactions
The analysis of the results in Table 2 shows that titanium dioxide has good catalytic activity, and the activity of the noble metal-supported titanium dioxide is improved, and the process can be performed in the visible light range. The catalyst such as bismuth tungstate and cadmium oxide has better catalytic effect.
Examples 30 to 41, a quantity of different substrates, 5mg TiO 2 2mL of acetonitrile is added into a 10mL photoreactor, the reactor is closed, the reaction temperature is room temperature, and the reaction is carried out for a certain time under the illumination condition of 365nm and 40W. The qualitative analysis of the obtained sample adopts a gas chromatography-mass spectrometry combined technology, the quantitative analysis is realized by gas chromatography, and the result is shown in Table 3.
TABLE 3 catalytic reaction Effect of different reaction substrates and amounts thereof
Analysis of the results in Table 3 shows that all of the 8 substrates tested had good reactivity.
The qualitative analysis of the product adopts gas chromatography-mass spectrometry, and the qualitative analysis is compared with the retention time of a standard sample; quantitative analysis was performed by internal standard gas chromatography.
Conversion = (number of moles of 2-tetrahydrofurfuryl acid converted/number of moles of 2-tetrahydrofurfuryl acid added and its derivative ester) ×100%
Selectivity = (moles of 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and its derivative ester/moles of converted 2-tetrahydrofurfuryl acid and its derivative ester) ×100%.
Claims (10)
1. The preparation method of biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative esters thereof is characterized in that the method adopts a photocatalysis method, and under the irradiation of ultraviolet light or visible light, a semiconductor catalyst is utilized to carry out C-C coupling reaction, so that 2-tetrahydrofurfuryl acid and derivative esters thereof are converted into 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative esters thereof.
2. The method for producing biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative esters thereof according to claim 1, wherein the structural formula of the 2-tetrahydrofurfuryl acid and derivative esters thereof is The structural formula of the product 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and the derivative ester thereof is
3. The method for preparing biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative esters thereof according to claim 1, wherein the wavelength of ultraviolet light or visible light ranges from 300 nm to 800nm.
4. The method for producing biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and its derivative ester according to claim 1, wherein the semiconductor catalyst comprises a titanium-based semiconductor catalyst, a bismuth-based semiconductor catalyst or a cadmium-based semiconductor catalyst.
5. The method for producing biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and ester derived therefrom according to claim 4, wherein the titanium-based semiconductor catalyst is titanium dioxide, cu/TiO of titanium dioxide supported by excessive noble metal or noble metal 2 、Au/TiO 2 、Ru/TiO 2 。
6. The method for producing biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and its derivative ester according to claim 4, wherein the bismuth-based semiconductor catalyst is bismuth oxide, bismuth trioxide, bismuth tungstate, and transition metal or noble metal-supported bismuth tungstate.
7. The method for producing biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and its derivative ester according to claim 4, wherein the cadmium semiconductor catalyst is cadmium oxide, cadmium sulfide, cadmium carbonate, and transition metal or noble metal-supported cadmium oxide, cadmium sulfide.
8. The method for preparing biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative esters thereof according to claim 1, wherein the reaction temperature is 10-30 ℃; the reaction time is 0.5-48h.
9. The method for preparing biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and its derivative ester according to claim 1, wherein the mass ratio of the semiconductor catalyst to the 2-tetrahydrofurfuryl acid and its derivative ester is: 0.1-10wt%.
10. The method for preparing biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative esters thereof according to claim 1, wherein the solvent is one or more of toluene, o-xylene, acetonitrile, dichloromethane and dimethyl sulfoxide, or the solvent is not added in the reaction; stirring is carried out during the reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311160574.0A CN117384115A (en) | 2023-09-11 | 2023-09-11 | Preparation method of biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative ester thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311160574.0A CN117384115A (en) | 2023-09-11 | 2023-09-11 | Preparation method of biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative ester thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117384115A true CN117384115A (en) | 2024-01-12 |
Family
ID=89438044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311160574.0A Pending CN117384115A (en) | 2023-09-11 | 2023-09-11 | Preparation method of biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative ester thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117384115A (en) |
-
2023
- 2023-09-11 CN CN202311160574.0A patent/CN117384115A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105330523A (en) | Method for preparing cyclopentanone by taking biomass resource as raw material | |
| US20200181058A1 (en) | Method for Preparing P-Hydroxycinnamate by Using Ionic Liquid for Catalytic Lignin Depolymerization | |
| CN110368928B (en) | Catalyst for synthesizing benzaldehyde by oxidizing benzyl alcohol and preparation method and application thereof | |
| CN113117688A (en) | MOF precursor molybdenum-nickel catalyst, preparation method thereof and application thereof in lignin degradation | |
| CN108409692A (en) | A kind of method that the carbon material supported ruthenium catalyst catalysis levulic acid Hydrogenation of sulfur doping takes gamma-valerolactone | |
| CN107286006B (en) | Method for preparing vanillone and acetosyringone by catalytic alcoholysis of lignin | |
| CN112371185A (en) | Polyacid catalyst and preparation method and application thereof | |
| CN117384115A (en) | Preparation method of biomass-based 2,2 '-bistetrahydrofuran-2, 2' -dicarboxylic acid and derivative ester thereof | |
| CN115138392B (en) | Multifunctional biochar catalyst rich in oxygen-containing functional groups and preparation method thereof | |
| CN111087371A (en) | Photocatalytic synthesis method of 2, 5-furan dicarbaldehyde | |
| CN113845500B (en) | Method for preparing 5-formyl-2-furancarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural | |
| CN115739093A (en) | Catalyst for preparing 2, 5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural and preparation method thereof | |
| CN111389453B (en) | Method for converting high-concentration lignin into cycloparaffin by liquid phase | |
| CN111744553B (en) | Zirconium dodecylbenzene sulfonate catalyst and application thereof in furfuryl alcohol alcoholysis reaction | |
| CN111434657B (en) | Preparation method of gamma-valerolactone and levulinate ester compound | |
| CN101624330A (en) | Method for preparing 1,4-butanediol through hydrogenation of cis-butenedioic acid dimethyl ester | |
| CN1781899A (en) | Process for preparing ethyl acetate from ethanol | |
| CN110526882B (en) | Furan tetramer and synthesis method thereof | |
| CN112812000B (en) | Preparation method of maleic acid | |
| CN115385882B (en) | Method for preparing delta-caprolactone | |
| CN112375052B (en) | Method for preparing 2, 5-diformylfuran through glucose three-step cascade reaction | |
| CN118142522B (en) | Preparation method of metal oxide/ruthenium-tungsten composite catalyst and application of catalyst in catalyzing C-O bond cracking in lignin | |
| CN114907296B (en) | Method for efficiently catalyzing succinic acid to dehydrate to generate succinic anhydride | |
| CN115608409B (en) | Magnesium-aluminum composite oxide/HZSM-5 dual-function catalyst and preparation method and application thereof | |
| CN114524787B (en) | Catalytic oxidative coupling method for methyl furoate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |