CN107267687B - Cellulose degradation method based on supported perrhenate ionic liquid - Google Patents
Cellulose degradation method based on supported perrhenate ionic liquid Download PDFInfo
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- CN107267687B CN107267687B CN201710485591.XA CN201710485591A CN107267687B CN 107267687 B CN107267687 B CN 107267687B CN 201710485591 A CN201710485591 A CN 201710485591A CN 107267687 B CN107267687 B CN 107267687B
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 95
- 229920002678 cellulose Polymers 0.000 title claims abstract description 44
- 239000001913 cellulose Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 37
- 230000015556 catabolic process Effects 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000010980 cellulose Nutrition 0.000 claims description 41
- 238000001914 filtration Methods 0.000 claims description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 26
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- DECWYWSYTFTUAV-UHFFFAOYSA-N 1-methyl-2-propylimidazole Chemical compound CCCC1=NC=CN1C DECWYWSYTFTUAV-UHFFFAOYSA-N 0.000 claims description 13
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 12
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 12
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 12
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- PBIDWHVVZCGMAR-UHFFFAOYSA-N 1-methyl-3-prop-2-enyl-2h-imidazole Chemical compound CN1CN(CC=C)C=C1 PBIDWHVVZCGMAR-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 5
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 claims description 5
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 4
- -1 chloropropyl triethoxysilane imidazole Chemical compound 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 229920000875 Dissolving pulp Polymers 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 12
- 239000008103 glucose Substances 0.000 description 12
- 238000007865 diluting Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 240000008042 Zea mays Species 0.000 description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 4
- 235000005822 corn Nutrition 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000010902 straw Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010907 stover Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QVRCRKLLQYOIKY-UHFFFAOYSA-M 1-methyl-3-prop-2-enylimidazol-1-ium;chloride Chemical compound [Cl-].C[N+]=1C=CN(CC=C)C=1 QVRCRKLLQYOIKY-UHFFFAOYSA-M 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000003282 rhenium compounds Chemical class 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Catalysts (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to a cellulose degradation method based on a supported perrhenate ionic liquid. The technical scheme is as follows: dissolving cellulose in ionic liquid solvent with anion as ReO4 ‑The supported perrhenate ionic liquid is used as a catalyst for degradation. The degradation reaction temperature is 120-170 ℃, and the reaction time is 10-60 min. After the reaction is finished, water is added to dilute the reaction solution, and the reaction solution is filtered and separated. The method is simple, the catalyst is environment-friendly and easy to recycle, and the cellulose degradation effect is good.
Description
Technical Field
The invention belongs to the field of cellulose degradation methods, and particularly relates to a cellulose degradation method based on a supported perrhenate ionic liquid.
Background
China is a large energy consumption country, and social and economic sustainable development is difficult to realize by only relying on fossil energy. Biomass is widely distributed on the earth and is the only renewable energy source capable of being produced physically like coal, oil and natural gas to form a huge industry. China is a big agricultural country, and the agricultural and forestry biomass resources such as straws are rich. The development of biomass energy and the improvement of the energy structure in China are not only the requirements of low-carbon environmental protection development, but also the necessary guarantee of future energy supply.
Cellulose is an important component of lignocellulose and can generate various platform compounds after being degraded. Hydrochloric acid, sulfuric acid and other strong acids and cellulase are traditional catalysts for cellulose degradation. But the problems of unstable enzyme catalytic activity, acid catalytic corrosion of equipment, serious environmental pollution and the like exist in the using process. Therefore, it is necessary to find a green and efficient cellulose degradation method. The metal rhenium compound is a novel multifunctional catalytic material, and is widely applied to catalyzing various organic chemical reactions because the compound has the advantages of simple synthesis method, environmental friendliness, easy recovery and reuse and the like. The cellulose molecular structure has a large number of hydroxyl groups, glucose structural units of the cellulose molecular structure are connected together through the interaction between beta-1, 4-glycosidic bonds and the hydroxyl groups to form a compact supramolecular system, and the key of the cellulose degradation process is beta-1, 4-Cleavage of glycosidic bonds and hydroxyl groups. And ReO4 -The Re (O) can form stronger hydrogen bond action with hydrogen bonds in cellulose molecules, is favorable for the breakage of beta-1, 4-glycosidic bonds and hydroxyl groups in the cellulose molecules, and enables perrhenate to become an effective catalyst for cellulose degradation. However, the perrhenate and the cellulose can be dissolved in the solvent ionic liquid together, so that the catalyst is not beneficial to recovery and reuse, and the cost of the catalyst is greatly increased.
Disclosure of Invention
The invention aims to provide a cellulose degradation method based on a supported perrhenate ionic liquid, which is simple, environment-friendly and easy to recycle as a catalyst and good in cellulose degradation effect.
The technical scheme adopted by the invention is as follows: a cellulose degradation method based on a supported perrhenate ionic liquid comprises the following steps: dissolving a proper amount of cellulose in an ionic liquid solvent, adding a proper amount of supported perrhenate ionic liquid catalyst after dissolving at 90-110 ℃, reacting for 10-60 min at 120-170 ℃, adding water to dilute reaction liquid after the reaction is finished, and filtering.
The above method for degrading cellulose based on supported perrhenate ionic liquid is as follows: based on ReO with the structural formula shown as (I)4 -Anion supported perrhenate ionic liquid or ReO-based ionic liquid with structural formula shown as (II)4 -Anion supported sulfonic acid functionalized perrhenate ionic liquid or ReO-based ionic liquid with structural formula shown as (III)4 -Anion supported carboxylic acid functionalized perrhenate ionic liquid;
wherein n is an integer of 0 to 8.
The method for degrading cellulose based on supported perrhenate ionic liquid is based on ReO4 -The anion supported sulfonic acid functionalized perrhenate ionic liquid is 1- (3-sulfonic acid)Acid) propyl-3-methylimidazole perrhenate ionic liquid; the preparation method comprises the following steps: adding an MCM-41 molecular sieve and chloropropyltriethoxysilane into an organic solvent, stirring for 1-24 h at 20-200 ℃, adding imidazole, continuing stirring for 1-24 h, filtering and drying to obtain an intermediate A; placing the intermediate A and 1, 3-propane sultone in an organic solvent, carrying out reflux reaction at 70 ℃ for 24h, cooling, filtering, washing with diethyl ether, and carrying out vacuum drying at 50 ℃ for 8h to obtain an ionic liquid intermediate B; adding the ionic liquid intermediate B and 37% concentrated hydrochloric acid into a certain amount of organic solvent, reacting for 12h at 70 ℃, and filtering after complete reaction to obtain an intermediate C; and adding the intermediate C and ammonium perrhenate into an organic solvent, stirring for 1-24 h at room temperature, filtering, and drying to obtain the 1- (3-sulfonic acid) propyl-3-methylimidazole perrhenate ionic liquid.
According to the cellulose degradation method based on the supported perrhenate ionic liquid, chloropropyl triethoxysilane MCM-41 molecular sieve is 1: 1-1: 3, chloropropyl triethoxysilane imidazole is 1: 1-1: 3, intermediate A is 1:1, 3-propane sultone is 1: 1-1: 4, intermediate B is concentrated hydrochloric acid is 1: 1-1: 2, and intermediate C is ammonium perrhenate is 1: 1-1: 1.5 according to the mol ratio.
The method for degrading cellulose based on supported perrhenate ionic liquid is based on ReO4 -The anion supported carboxylic acid functionalized perrhenate ionic liquid is 1- (alpha-carboxylic acid) methyl-3-methylimidazole perrhenate ionic liquid; the preparation method comprises the following steps: adding an MCM-41 molecular sieve and chloropropyltriethoxysilane into an organic solvent, stirring for 1-24 h at 20-200 ℃, adding imidazole, continuing stirring for 1-24 h, filtering and drying to obtain an intermediate A; dissolving the intermediate A and ethyl chloroacetate in an organic solvent, carrying out reflux reaction at 70 ℃ for 24h, cooling, filtering, washing with diethyl ether, and carrying out vacuum drying at 50 ℃ for 8h to obtain an ionic liquid intermediate B; adding the ionic liquid intermediate B and 37% concentrated hydrochloric acid into an organic solvent, reacting for 12h at 70 ℃, cooling, filtering, washing with diethyl ether, and drying in vacuum to obtain an intermediate C; adding the intermediate C and ammonium perrhenate into an organic solvent, stirring for 1-24 h at room temperature, filtering, and drying to obtain 1- (alpha-carboxyl)Acid) methyl-3-methylimidazole perrhenate ionic liquid.
According to the cellulose degradation method based on the supported perrhenate ionic liquid, chloropropyl triethoxysilane is MCM-41 molecular sieve which is 1: 1-1: 3, chloropropyl triethoxysilane is imidazole which is 1: 1-1: 3, an intermediate A is ethyl chloroacetate which is 1: 1-1: 4, an intermediate B is concentrated hydrochloric acid which is 1: 1-1: 2, and an intermediate C is ammonium perrhenate which is 1: 1-1: 1.5 according to a molar ratio.
In the above method for degrading cellulose based on supported perrhenate ionic liquid, the organic solvent is ethanol, methanol, acetonitrile, toluene or ethyl acetate.
In the above method for degrading cellulose based on supported perrhenate ionic liquid, the ionic liquid solvent is that the anion is selected from Cl-、CH3COO-And RPO2 -The cation is selected from [ C ]nmim]+、[R4N]+And [ Cnpy]+N is 1 to 8, and R is methyl, ethyl, n-butyl or n-hexadecyl. Preferably, the ionic liquid solvent is 1-allyl-3-methylimidazole chloride salt.
According to the cellulose degradation method based on the supported perrhenate ionic liquid, the mass ratio of cellulose to the ionic liquid solvent is 1: 5-40, and the addition amount of the supported perrhenate ionic liquid is 10% -100% of the mass of the cellulose.
In the above method for degrading cellulose based on supported perrhenate ionic liquid, the cellulose is microcrystalline cellulose or lignocellulose; or cellulose derived from rice straw and stalks.
The invention has the beneficial effects that:
1. the invention will be based on ReO4 -The anionic supported perrhenate ionic liquid is used for cellulose degradation for the first time, and the catalyst is high in activity, green, environment-friendly and good in cellulose degradation effect.
2. The invention takes the ionic liquid as the solvent to degrade the lignocellulose, directly adds water for dilution after the reaction, and can separate the catalyst by filtering, and the treatment method is simple.
3. The supported perrhenate ionic liquid used in the invention has stable chemical properties, and the separated catalyst can be repeatedly used for more than 5 times after being washed and dried, and the catalytic effect is not obviously reduced.
4. The supported perrhenate ionic liquid used in the invention has no pollution to the environment, and can relieve the problems of equipment corrosion, environmental pollution and the like caused in the use process of acid catalysts such as inorganic acid, acid functional ionic liquid and the like.
5. According to the invention, after the reaction is finished, the catalyst can be directly filtered and separated, washed by ether and dried for reuse. The glucose yield after 5 uses is still higher than 35.0%.
6. According to the invention, the perrhenate ionic liquid is loaded by a chemical method, and the obtained loaded perrhenate ionic liquid is used for lignocellulose degradation reaction, so that higher glucose yield is obtained.
Detailed Description
The present invention will be described in further detail with reference to examples, which are not intended to limit the scope of the present invention.
Example 1 catalytic degradation of microcrystalline cellulose by Supported N-methylimidazole perrhenate Ionic liquid
The structural formula of the supported N-methylimidazole perrhenate ionic liquid is shown as the following formula:
0.1g of microcrystalline cellulose and 2.0g of 1-allyl-3-methylimidazole chloride ionic liquid are weighed into a 10mL reaction bottle, uniformly stirred, dissolved at 100 ℃ for 10min, added with 0.05g of supported N-methylimidazole perrhenate ionic liquid and 70 mu L of water, and heated at 150 ℃ for 30 min. After the reaction, the reaction solution was diluted with water and filtered, the filtrate was diluted to 100mL, TRS was measured by DNS method, and the reaction product was analyzed by high performance liquid chromatography, whereby TRS was 78.5.9%, and the yield of glucose was 39.3%.
Example 2 Supported 1- (3-sulfonic acid) propyl-3-methylimidazole perrhenate Ionic liquid catalyzed degradation of microcrystalline cellulose
(I) load type 1- (3-sulfonic acid) propyl-3-methylimidazole perrhenate ionic liquid
The structural formula is shown as the following formula:
the preparation method comprises the following steps:
adding 2.0g of MCM-41 molecular sieve and 1.0g of chloropropyltriethoxysilane into 25mL of toluene, stirring for 12h at 60 ℃, adding 1.0g of imidazole, continuing stirring for 12h, filtering and drying to obtain an intermediate A; placing the intermediate A and 1.0g of 1, 3-propane sultone in 25mL of toluene, carrying out reflux reaction at 70 ℃ for 24h, cooling, filtering, washing with diethyl ether, and carrying out vacuum drying at 50 ℃ for 8h to obtain an ionic liquid intermediate B; adding the ionic liquid intermediate B and 5mL of 37% concentrated hydrochloric acid into 25mL of toluene, reacting for 12h at 70 ℃, and filtering after complete reaction to obtain an intermediate C; and adding the intermediate C and 0.5g of ammonium perrhenate into 25mL of toluene solvent, stirring for 24h at room temperature, filtering and drying to obtain the 1- (3-sulfonic acid) propyl-3-methylimidazole perrhenate ionic liquid.
(II) catalytic degradation of microcrystalline cellulose
0.1g of microcrystalline cellulose and 2.0g of 1-allyl-3-methylimidazole chloride ionic liquid are weighed into a 10mL reaction flask, uniformly stirred, dissolved at 100 ℃ for 10min, added with 0.05g of supported 1- (3-sulfonic acid) propyl-3-methylimidazole perrhenate ionic liquid and 70 mu L of water, and heated at 150 ℃ for 30 min. Diluting the reaction solution with water, filtering, diluting the filtrate to 100mL, determining TRS by a DNS method, and analyzing the reaction product by high performance liquid chromatography to determine that the TRS is 88.9% and the glucose yield is 45.1%.
The filtered catalyst was washed with ether, dried and reused, with five glucose yields of 45.1%, 45.4%, 42.6%, 41.5% and 40.2%, respectively.
Example 3 Supported 1- (. alpha. -carboxylic acid) methyl-3-methylimidazole perrhenate Ionic liquid catalyzed degradation of microcrystalline cellulose
(mono) supported 1- (alpha-carboxylic acid) methyl-3-methylimidazole perrhenate ionic liquid
The structural formula is shown as the following formula:
the preparation method comprises the following steps:
adding 2.0g of MCM-41 molecular sieve and 1.0g of chloropropyltriethoxysilane into 25mL of toluene, stirring for 12h at 60 ℃, adding 1.0g of imidazole, continuing stirring for 12h, filtering and drying to obtain an intermediate A; placing the intermediate A and 1.0g of ethyl chloroacetate in 25mL of toluene, carrying out reflux reaction at 70 ℃ for 24h, cooling, filtering, washing with diethyl ether, and carrying out vacuum drying at 50 ℃ for 8h to obtain an ionic liquid intermediate B; adding the ionic liquid intermediate B and 5mL of 37% concentrated hydrochloric acid into 25mL of toluene, reacting for 12h at 70 ℃, and filtering after complete reaction to obtain an intermediate C; and adding the intermediate C and 0.5g of ammonium perrhenate into 25mL of toluene solvent, stirring for 24h at room temperature, filtering and drying to obtain the 1- (alpha-carboxylic acid) methyl-3-methylimidazole perrhenate ionic liquid.
(II) catalytic degradation of microcrystalline cellulose
0.1g of microcrystalline cellulose and 2.0g of 1-allyl-3-methylimidazole chloride ionic liquid are weighed into a 10mL reaction flask, uniformly stirred, dissolved at 100 ℃ for 10min, added with 0.05g of supported 1- (alpha-carboxylic acid) methyl-3-methylimidazole perrhenate ionic liquid and 70 mu L of water, and heated at 150 ℃ for 30 min. Diluting the reaction solution with water, filtering, diluting the filtrate to 100mL, determining TRS by DNS method, and analyzing the reaction product by high performance liquid chromatography to determine TRS of 85.6% and glucose yield of 43.2%.
The filtered catalyst was washed with ether, dried and reused, with five glucose yields of 43.2%, 42.1%, 40.5%, 39.6% and 38.8%, respectively.
Example 4 Supported 1- (3-sulfonic acid) propyl-3-methylimidazole perrhenate Ionic liquid catalyzed degradation of steam explosion treated corn stover
0.1g of corn straw subjected to steam explosion treatment and 2.0g of 1-allyl-3-methylimidazole chloride ionic liquid are weighed into a 10mL reaction bottle, uniformly stirred, dissolved at 100 ℃ for 10min, added with 0.05g of supported 1- (3-sulfonic acid) propyl-3-methylimidazole perrhenate ionic liquid and 70 mu L of water, and heated at 150 ℃ for 30 min. Diluting the reaction solution with water, filtering, diluting the filtrate to 100mL, determining TRS by a DNS method, and analyzing the reaction product by high performance liquid chromatography to determine TRS to be 75.6% and glucose yield to be 44.5%.
Example 5 degradation of corn stover by Supported 1- (3-sulfonic acid) propyl-3-methylimidazole perrhenate Ionic liquid
0.1g of corn straw and 2.0g of 1-allyl-3-methylimidazole chloride ionic liquid are weighed in a 10mL reaction bottle, uniformly stirred, dissolved at 100 ℃ for 10min, added with 0.05g of supported 1- (3-sulfonic acid) propyl-3-methylimidazole perrhenate ionic liquid and 70 mu L of water, and heated at 150 ℃ for 30 min. Diluting the reaction solution with water, filtering, diluting the filtrate to 100mL, determining TRS by DNS method, and analyzing the reaction product by high performance liquid chromatography to determine TRS is 77.6% and glucose yield is 37.9%.
Comparative example 1
0.1g of microcrystalline cellulose is placed in 2.0g of 1-allyl-3-methylimidazolium chloride ionic liquid and dissolved at 100 ℃ for 10min, 70. mu.L of water is added and the mixture is heated at 150 ℃ for 30 min. Diluting the reaction solution with water, filtering, diluting the filtrate to 100mL, determining TRS by a DNS method, and analyzing the reaction product by high performance liquid chromatography to determine that the TRS is 16.3% and the glucose yield is 5.4%.
The above examples show that the lignocellulose degradation method based on the supported perrhenate ionic liquid catalyst can sufficiently degrade cellulose to obtain higher yield of glucose. The catalytic process avoids the use of traditional strong acid catalysts, the reaction process and the catalyst separation operation are simple and easy, and a new process route is provided for the degradation and conversion of lignocellulose.
Claims (7)
1. A cellulose degradation method based on a supported perrhenate ionic liquid is characterized by comprising the following steps: dissolving a proper amount of microcrystalline cellulose in 1-allyl-3-methylimidazole chloride ionic liquid, dissolving at 90-110 ℃, adding a proper amount of supported perrhenate ionic liquid catalyst, reacting at 150 ℃ for 30min, adding water to dilute reaction liquid after the reaction is finished, and filtering; the supported perrhenate ionic liquid is as follows:
structural formula is
The supported N-methylimidazole perrhenate ionic liquid,
Or structural formula
The supported 1- (3-sulfonic acid) propyl-3-methylimidazole perrhenate ionic liquid,
Or structural formula
The supported 1- (alpha-carboxylic acid) methyl-3-methylimidazole perrhenate ionic liquid.
2. The cellulose degradation method based on the supported perrhenate ionic liquid as claimed in claim 1, characterized in that: the preparation method of the supported 1- (3-sulfonic acid) propyl-3-methylimidazole perrhenate ionic liquid comprises the following steps: adding an MCM-41 molecular sieve and chloropropyltriethoxysilane into an organic solvent, stirring for 1-24 h at 20-200 ℃, adding imidazole, continuing stirring for 1-24 h, filtering and drying to obtain an intermediate A; placing the intermediate A and 1, 3-propane sultone in an organic solvent, carrying out reflux reaction at 70 ℃ for 24h, cooling, filtering, washing with diethyl ether, and carrying out vacuum drying at 50 ℃ for 8h to obtain an ionic liquid intermediate B; adding the ionic liquid intermediate B and 37% concentrated hydrochloric acid into a certain amount of organic solvent, reacting for 12h at 70 ℃, and filtering after complete reaction to obtain an intermediate C; and adding the intermediate C and ammonium perrhenate into an organic solvent, stirring for 1-24 h at room temperature, filtering, and drying to obtain the 1- (3-sulfonic acid) propyl-3-methylimidazole perrhenate ionic liquid.
3. The cellulose degradation method based on the supported perrhenate ionic liquid as claimed in claim 2, characterized in that: according to a molar ratio, chloropropyl triethoxysilane MCM-41 molecular sieve is 1: 1-1: 3, chloropropyl triethoxysilane imidazole is 1: 1-1: 3, intermediate A is 1:1, 3-propane sultone is 1: 1-1: 4, intermediate B is concentrated hydrochloric acid is 1: 1-1: 2, and intermediate C is ammonium perrhenate is 1: 1-1: 1.5.
4. The cellulose degradation method based on the supported perrhenate ionic liquid as claimed in claim 1, characterized in that: the preparation method of the supported 1- (alpha-carboxylic acid) methyl-3-methylimidazole perrhenate ionic liquid comprises the following steps: adding an MCM-41 molecular sieve and chloropropyltriethoxysilane into an organic solvent, stirring for 1-24 h at 20-200 ℃, adding imidazole, continuing stirring for 1-24 h, filtering and drying to obtain an intermediate A; dissolving the intermediate A and ethyl chloroacetate in an organic solvent, carrying out reflux reaction at 70 ℃ for 24h, cooling, filtering, washing with diethyl ether, and carrying out vacuum drying at 50 ℃ for 8h to obtain an ionic liquid intermediate B; adding the ionic liquid intermediate B and 37% concentrated hydrochloric acid into an organic solvent, reacting for 12h at 70 ℃, cooling, filtering, washing with diethyl ether, and drying in vacuum to obtain an intermediate C; and adding the intermediate C and ammonium perrhenate into an organic solvent, stirring for 1-24 h at room temperature, filtering, and drying to obtain the 1- (alpha-carboxylic acid) methyl-3-methylimidazole perrhenate ionic liquid.
5. The cellulose degradation method based on the supported perrhenate ionic liquid as claimed in claim 4, wherein the method comprises the following steps: according to a molar ratio, chloropropyl triethoxysilane to MCM-41 molecular sieve is 1: 1-1: 3, chloropropyl triethoxysilane to imidazole is 1: 1-1: 3, an intermediate A to ethyl chloroacetate is 1: 1-1: 4, an intermediate B to concentrated hydrochloric acid is 1: 1-1: 2, and an intermediate C to ammonium perrhenate is 1: 1-1: 1.5.
6. The cellulose degradation method based on the supported perrhenate ionic liquid as claimed in claim 2 or 4, wherein: the organic solvent is ethanol, methanol, acetonitrile, toluene or ethyl acetate.
7. The cellulose degradation method based on the supported perrhenate ionic liquid as claimed in claim 1, characterized in that: the mass ratio of the microcrystalline cellulose to the 1-allyl-3-methylimidazole chloride ionic liquid is 1: 5-40, and the addition amount of the supported perrhenate ionic liquid is 10-100% of the mass of the cellulose.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450088A (en) * | 2013-09-22 | 2013-12-18 | 辽宁石油化工大学 | Novel sulfonic acid functionalized rhenium ionic liquid and preparation method and application thereof |
| CN103467384A (en) * | 2013-09-22 | 2013-12-25 | 辽宁石油化工大学 | Novel carboxylic acid functional rhenium iron liquid and preparation method and application thereof |
| CN103464200A (en) * | 2013-09-22 | 2013-12-25 | 辽宁石油化工大学 | Supported perrhenate ionic liquid as well as preparation method thereof |
| CN105618139A (en) * | 2016-03-23 | 2016-06-01 | 辽宁石油化工大学 | Method for degrading lignocellulose based on molybdenum polyoxometallate |
| CN106045913A (en) * | 2016-06-06 | 2016-10-26 | 辽宁大学 | Imidazolium perrhenate ionic liquid with amino groups as well as preparation method and application of imidazolium perrhenate ionic liquid |
| CN106146320A (en) * | 2015-04-10 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of quaternary ammonium salt perrhenate ions liquid and synthetic method thereof and application |
-
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- 2017-06-23 CN CN201710485591.XA patent/CN107267687B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450088A (en) * | 2013-09-22 | 2013-12-18 | 辽宁石油化工大学 | Novel sulfonic acid functionalized rhenium ionic liquid and preparation method and application thereof |
| CN103467384A (en) * | 2013-09-22 | 2013-12-25 | 辽宁石油化工大学 | Novel carboxylic acid functional rhenium iron liquid and preparation method and application thereof |
| CN103464200A (en) * | 2013-09-22 | 2013-12-25 | 辽宁石油化工大学 | Supported perrhenate ionic liquid as well as preparation method thereof |
| CN106146320A (en) * | 2015-04-10 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of quaternary ammonium salt perrhenate ions liquid and synthetic method thereof and application |
| CN105618139A (en) * | 2016-03-23 | 2016-06-01 | 辽宁石油化工大学 | Method for degrading lignocellulose based on molybdenum polyoxometallate |
| CN106045913A (en) * | 2016-06-06 | 2016-10-26 | 辽宁大学 | Imidazolium perrhenate ionic liquid with amino groups as well as preparation method and application of imidazolium perrhenate ionic liquid |
Non-Patent Citations (1)
| Title |
|---|
| "Hydrolysis of cellulose catalyzed by quaternary ammonium perrhenates in 1-allyl-3-methylimidazolium chloride";Wang J Y. et al;《Bioresource Technology》;20150804;第197卷;第43页、第45页表2及supporting information 第4页 * |
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