CN107267687A - A kind of cellulose degradation method based on support type perrhenate ions liquid - Google Patents
A kind of cellulose degradation method based on support type perrhenate ions liquid Download PDFInfo
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- CN107267687A CN107267687A CN201710485591.XA CN201710485591A CN107267687A CN 107267687 A CN107267687 A CN 107267687A CN 201710485591 A CN201710485591 A CN 201710485591A CN 107267687 A CN107267687 A CN 107267687A
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- China
- Prior art keywords
- support type
- perrhenate
- ions liquid
- perrhenate ions
- cellulose
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- 239000007788 liquid Substances 0.000 title claims abstract description 79
- 150000002500 ions Chemical class 0.000 title claims abstract description 76
- 229920002678 cellulose Polymers 0.000 title claims abstract description 49
- 239000001913 cellulose Substances 0.000 title claims abstract description 49
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000015556 catabolic process Effects 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001450 anions Chemical class 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 235000010980 cellulose Nutrition 0.000 claims description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000002608 ionic liquid Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 18
- 238000001914 filtration Methods 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
- 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
- 150000002460 imidazoles Chemical class 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
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 9
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 8
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 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
- 239000010902 straw Substances 0.000 claims description 6
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 5
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- -1 chloropropyl Chemical group 0.000 claims description 4
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004090 dissolution Methods 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 240000008042 Zea mays Species 0.000 description 4
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 235000009973 maize Nutrition 0.000 description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052702 rhenium Inorganic materials 0.000 description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 3
- 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
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003912 environmental pollution 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
- 239000000126 substance Substances 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- RSMCZIMSRVMJEB-UHFFFAOYSA-N [Cl].CCOC(C)=O Chemical compound [Cl].CCOC(C)=O RSMCZIMSRVMJEB-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement 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
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003282 rhenium compounds Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- 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 present invention relates to a kind of cellulose degradation method based on support type perrhenate ions liquid.The technical scheme of use is：By cellulose dissolution in ion liquid solvent, using anion as ReO4 ‑Support type perrhenate ions liquid degraded for catalyst.Degradation reaction temperature is in 120~170 DEG C, 10~60min of reaction time.Reaction adds water after terminating to be diluted reaction solution, filters, separating.The inventive method is simple, catalyst environmental protection and easily reclaim, cellulose degradation effect it is good.
Description
Technical field
The invention belongs to cellulose degradation method field, and in particular to a kind of based on support type perrhenate ions liquid
Cellulose degradation method.
Background technology
China is an energy-consuming big country, simple to be difficult to society and economic sustainable development by fossil energy
Exhibition.Biomass is widely distributed on earth, is that unique one kind can carry out materiality as coal, oil and natural gas and produce to be formed
The regenerative resource of huge enterprise.China is large agricultural country, the agricultural-forestry biomass aboundresources such as stalk.Biomass Energy Development is simultaneously
The need for improvement China energy resource structure is not only low-carbon environment-friendly development, and it is also the necessary guarantee of future energy supply.
Cellulose is the important component of lignocellulosic, and kinds of platform compound can be generated after degraded.Hydrochloric acid, sulfuric acid
It is the traditional catalyst of cellulose degradation Deng strong acid and cellulase.But it is unstable to there is enzymatic activity during use, and acid is urged
Change the problems such as etching apparatus and serious environmental pollution.Thus, it is found that a kind of green, efficient cellulose degradation method very must
Will.Metal rhenium compound is new multi-functional catalysis material, and because such compound has, synthetic method is simple, environment is friendly
It is good, easy to reclaim the advantages of reusing, it is widely used a variety of organic chemical reactionses of catalysis.And deposited in cellulose molecular structure
In substantial amounts of hydroxyl, its glucose building blocks is to be connected to one by β-Isosorbide-5-Nitrae-interaction between glycosidic bond and hydroxyl
Rise, form fine and close supramolecular system, the key of cellulose degradation process is exactly the fracture of β-Isosorbide-5-Nitrae-glycosidic bond and hydroxyl.And
ReO4 -Re=O can with the stronger hydrogen bond action of hydrogen bond formation in cellulosic molecule, be conducive to β-Isosorbide-5-Nitrae in cellulosic molecule-
The fracture of glycosidic bond and hydroxyl, makes perrhenate turn into the effective catalyst of cellulose degradation.But perrhenate can be with cellulose
Lyate ion liquid is dissolved in together, is unfavorable for the recovery and reuse of catalyst, is greatly improved catalyst cost.
The content of the invention
It is an object of the invention to provide a kind of method is simple, catalyst environmental protection and easily reclaim, cellulose degradation effect
The really good cellulose degradation method based on support type perrhenate ions liquid.
The technical solution adopted by the present invention is：A kind of cellulose degradation side based on support type perrhenate ions liquid
Method, comprises the following steps：Take appropriate cellulose to be dissolved in ion liquid solvent, after 90~110 DEG C dissolve, add appropriate load
Type perrhenate ions liquid catalyst, 10~60min is reacted at 120~170 DEG C, after reaction terminates, reaction solution is added water dilute
Release, filter.
A kind of above-mentioned cellulose degradation method based on support type perrhenate ions liquid, the high rhenium of described support type
Hydrochlorate ionic liquid is：Structural formula as shown in (I) based on ReO4 -The support type perrhenate ions liquid or structure of anion
Formula as shown in (II) based on ReO4 -The support type sulfonic acid funtionalized perrhenate ions liquid or structural formula such as (III) of anion
It is shown based on ReO4 -The support type carboxylic acid functional perrhenate ions liquid of anion；
Wherein, the integer of n=0~8.
A kind of above-mentioned cellulose degradation method based on support type perrhenate ions liquid, it is described based on ReO4 -It is cloudy
The support type sulfonic acid funtionalized perrhenate ions liquid of ion is 1- (3- sulfonic acid) propyl group -3- methylimidazole perrhenate ions
Liquid；Preparation method comprises the following steps：MCM-41 molecular sieves and chloropropyl triethoxysilane are added in organic solvent, in
20~200 DEG C of 1~24h of stirring, add imidazoles, continue to stir 1~24h, filter, dry, obtain intermediate A；By intermediate A and 1,
3- propane sultones are placed in organic solvent, 70 DEG C of back flow reaction 24h, are cooled down, filtering, and are washed with ether, at 50 DEG C
8h is dried in vacuo, ionic liquid intermediate B is obtained；Ionic liquid intermediate B and 37% are added in a certain amount of organic solvent
Concentrated hydrochloric acid, reacts 12h at 70 DEG C, after reaction completely, and filtering obtains intermediate C；In organic solvent add intermediate C and
Ammonium perrhenate, stirs 1~24h at room temperature, filters, and dries, obtains 1- (3- sulfonic acid) propyl group -3- methylimidazole perrhenate ions
Liquid.
A kind of above-mentioned cellulose degradation method based on support type perrhenate ions liquid, in molar ratio, chloropropyl
Triethoxysilane:MCM-41 molecular sieve=1:1~1:3rd, chloropropyl triethoxysilane:Imidazoles=1:1~1:3rd, intermediate
A:1,3- propane sultone=1:1~1:4th, intermediate B:Concentrated hydrochloric acid=1:1~1:2nd, intermediate C:Ammonium perrhenate=1:1~
1:1.5。
A kind of above-mentioned cellulose degradation method based on support type perrhenate ions liquid, it is described based on ReO4 -It is cloudy
The support type carboxylic acid functional perrhenate ions liquid of ion is 1- (α-carboxylic acid) methyl -3- methylimidazole perrhenate ions
Liquid；Preparation method comprises the following steps：MCM-41 molecular sieves and chloropropyl triethoxysilane are added in organic solvent, in
20~200 DEG C of 1~24h of stirring, add imidazoles, continue to stir 1~24h, filter, dry, obtain intermediate A；By intermediate A and chlorine
Ethyl acetate is dissolved in organic solvent, 70 DEG C of back flow reaction 24h, is cooled down, filtering, and is washed with ether, and vacuum is done at 50 DEG C
Dry 8h, obtains ionic liquid intermediate B；Ionic liquid intermediate B and 37% concentrated hydrochloric acid are added in organic solvent, at 70 DEG C
12h is reacted, is cooled down, filtering, and washed with ether, it is dried in vacuo, obtains intermediate C；In organic solvent add intermediate C and
Ammonium perrhenate, stirs 1~24h at room temperature, filters, and dries, obtains 1- (α-carboxylic acid) methyl -3- methylimidazole perrhenate ions
Liquid.
A kind of above-mentioned cellulose degradation method based on support type perrhenate ions liquid, in molar ratio, chloropropyl
Triethoxysilane:MCM-41 molecular sieve=1:1~1:3rd, chloropropyl triethoxysilane:Imidazoles=1:1~1:3rd, intermediate
A:Ethyl chloroacetate=1:1~1:4th, intermediate B:Concentrated hydrochloric acid=1:1~1:2nd, intermediate C:Ammonium perrhenate=1:1~1:1.5.
A kind of above-mentioned cellulose degradation method based on support type perrhenate ions liquid, described organic solvent is
Ethanol, methanol, acetonitrile, toluene or ethyl acetate.
A kind of above-mentioned cellulose degradation method based on support type perrhenate ions liquid, described ionic liquid is molten
Agent is that anion is selected from Cl-、CH3COO-And RPO2 -, cation is selected from [Cnmim]+、[R4N]+[Cnpy]+, n=1~8, R is
Methyl, ethyl, normal-butyl or n-hexadecyl.It is preferred that, described ion liquid solvent is 1- pi-allyl -3- methylimidazole chlorine
Salt.
A kind of above-mentioned cellulose degradation method based on support type perrhenate ions liquid, cellulose and ionic liquid
The mass ratio of solvent is 1:5~40, the addition based on support type perrhenate ions liquid for cellulose quality 10%~
100%.
A kind of above-mentioned cellulose degradation method based on support type perrhenate ions liquid, described cellulose is micro-
Crystalline cellulose or lignocellulosic；Or cellulose origin is in straw and stalk.
The beneficial effects of the invention are as follows：
1. the present invention, will be based on ReO4 -The support type perrhenate ions liquid of anion is used for cellulose degradation first,
Catalyst activity is high, and environmental protection, cellulose degradation effect is good.
2. the present invention, degrades to lignocellulosic by solvent of ionic liquid, be directly diluted with water after reaction, filter
Catalyst is may separate out, processing method is simple.
3. the present invention, used support type perrhenate ions aqueous chemical property is stable, the catalyst warp isolated
Reusable more than 5 times after washing, drying, catalytic effect is without obvious reduction.
4. the present invention, used support type perrhenate ions liquid is environmentally safe, inorganic acid, acid can be alleviated
The problems such as equipment corrosion that is brought during the acid catalyst use such as functional ion liquid, environmental pollution.
5. the present invention, reaction, which terminates rear catalyst, to be directly separated by filtration, and washed with ether, reusable after drying.
35.0% is remained above using glucose yield after 5 times.
6. the present invention, is loaded perrhenate ions liquid using chemical method, by obtained support type perrhenate
Ionic liquid reacts for ligocellulose degradation, obtains higher glucose yield.
Embodiment
Below by embodiment, the present invention is described in further detail, but embodiment is not the limit to the present invention
It is fixed.
The support type N- methylimidazole perrhenate ions liquid catalyst of embodiment 1 degraded microcrystalline cellulose
Support type N- methylimidazole perrhenate ions liquid structure formulas are shown below：
0.1g microcrystalline celluloses and 2.0g 1- pi-allyl -3- methylimidazoles chloride ion liquids are weighed in 10mL reaction bulb
In, after stirring, 100 DEG C dissolve 10min after, add 0.05g support type N- methylimidazole perrhenate ions liquid and
70 μ L water, 30min is heated at 150 DEG C.After reaction terminates, reaction solution is diluted with water and filtered, filtrate is settled to 100mL, is adopted
TRS is determined with DNS methods, and reaction product is analyzed using high performance liquid chromatography, TRS is measured for 78.5.9%, glucose
Yield is 39.3%.
Embodiment 2 support type 1- (3- sulfonic acid) propyl group -3- methylimidazole perrhenate ions liquid catalyst degraded crystallite is fine
Dimension element
(1) support type 1- (3- sulfonic acid) propyl group -3- methylimidazole perrhenate ions liquid
Structural formula is shown below：
Preparation method is as follows：
2.0g MCM-41 molecular sieves and 1.0g chloropropyl triethoxysilanes are added in 25mL toluene, in 60 DEG C of stirrings
12h, adds 1.0g imidazoles, continues to stir 12h, filters, dries, obtains intermediate A；By intermediate A and 1.0g1,3- propane sulfonic acids
Lactone is placed in 25mL toluene, 70 DEG C of back flow reaction 24h, is cooled down, filtering, and is washed with ether, and 8h is dried in vacuo at 50 DEG C,
Obtain ionic liquid intermediate B；Ionic liquid intermediate B and 5mL 37% concentrated hydrochloric acid are added in 25mL toluene, at 70 DEG C
12h is reacted, after reaction completely, filtering obtains intermediate C；Intermediate C and 0.5g perrhenic acid is added in 25mL toluene solvants
Ammonium, stirs 24h at room temperature, filters, and dries, obtains 1- (3- sulfonic acid) propyl group -3- methylimidazole perrhenate ions liquid.
(2) catalytic degradation microcrystalline cellulose
0.1g microcrystalline celluloses and 2.0g 1- pi-allyl -3- methylimidazoles chloride ion liquids are weighed in 10mL reaction bulb
In, after stirring, after 100 DEG C dissolve 10min, add the high rhenium of 0.05g support types 1- (3- sulfonic acid) propyl group -3- methylimidazoles
Hydrochlorate ionic liquid and 70 μ L water, 30min is heated at 150 DEG C.Reaction solution is diluted with water and filtered, and filtrate is settled to 100mL, adopts
TRS is determined with DNS methods, and reaction product is analyzed using high performance liquid chromatography, it is 88.9% to measure TRS, and glucose is received
Rate is 45.1%.
The catalyst filtered out is washed with ether, is reused after drying, is respectively using five glucose yields
45.1%th, 45.4%, 42.6%, 41.5% and 40.2%.
Embodiment 3 support type 1- (α-carboxylic acid) methyl -3- methylimidazole perrhenate ions liquid catalyst degraded crystallite is fine
Dimension element
(1) support type 1- (α-carboxylic acid) methyl -3- methylimidazole perrhenate ions liquid
Structural formula is shown below：
Preparation method is as follows：
2.0g MCM-41 molecular sieves and 1.0g chloropropyl triethoxysilanes are added in 25mL toluene, in 60 DEG C of stirrings
12h, adds 1.0g imidazoles, continues to stir 12h, filters, dries, obtains intermediate A；Intermediate A is put with 1.0g ethyl chloroacetates
In 25mL toluene, 70 DEG C of back flow reaction 24h are cooled down, filtering, and are washed with ether, are dried in vacuo 8h at 50 DEG C, are obtained ion
Liquid intermediate B；Ionic liquid intermediate B and 5mL 37% concentrated hydrochloric acid are added in 25mL toluene, is reacted at 70 DEG C
12h, after reaction completely, filtering obtains intermediate C；Intermediate C and 0.5g ammonium perrhenate is added in 25mL toluene solvants, in
24h is stirred at room temperature, is filtered, and is dried, is obtained 1- (α-carboxylic acid) methyl -3- methylimidazole perrhenate ions liquid.
(2) catalytic degradation microcrystalline cellulose
0.1g microcrystalline celluloses and 2.0g 1- pi-allyl -3- methylimidazoles chloride ion liquids are weighed in 10mL reaction bulb
In, after stirring, after 100 DEG C dissolve 10min, add the high rhenium of 0.05g support types 1- (α-carboxylic acid) methyl -3- methylimidazoles
Hydrochlorate ionic liquid and 70 μ L water, 30min is heated at 150 DEG C.Reaction solution is diluted with water and filtered, and filtrate is settled to 100mL, adopts
TRS is determined with DNS methods, and reaction product is analyzed using high performance liquid chromatography, it is 85.6% to measure TRS, and glucose is received
Rate is 43.2%.
The catalyst filtered out is washed with ether, is reused after drying, is respectively using five glucose yields
43.2%th, 42.1%, 40.5%, 39.6% and 38.8%.
Embodiment 4 support type 1- (3- sulfonic acid) propyl group -3- methylimidazole perrhenate ions liquid catalyst degraded steam is quick-fried
The maize straw of tear reason
Weigh the maize straw and 2.0g 1- pi-allyls -3- methylimidazoles chloride ion liquids of 0.1g Steam explosion treatments in
In 10mL reaction bulb, after stirring, after 100 DEG C dissolve 10min, 0.05g support types 1- (3- sulfonic acid) propyl group -3- is added
Methylimidazole perrhenate ions liquid and 70 μ L water, 30min is heated at 150 DEG C.Reaction solution is diluted with water and filtered, and filtrate is fixed
Hold to 100mL, TRS is determined using DNS methods, and reaction product is analyzed using high performance liquid chromatography, measuring TRS is
75.6%, glucose yield is 44.5%.
Embodiment 5 support type 1- (3- sulfonic acid) propyl group -3- methylimidazole perrhenate ions liquid catalyst degrading maize straw
Stalk
0.1g maize straws and 2.0g 1- pi-allyl -3- methylimidazoles chloride ion liquids are weighed in 10mL reaction bulb,
0.05g support types 1- (3- sulfonic acid) propyl group -3- methylimidazole perrhenates are added after dissolving 10min at 100 DEG C after stirring
Ionic liquid and 70 μ L water, 30min is heated at 150 DEG C.Reaction solution is diluted with water and filtered, and filtrate is settled to 100mL, uses
DNS methods determine TRS, and reaction product is analyzed using high performance liquid chromatography, and it is 77.6%, glucose yield to measure TRS
For 37.9%.
Comparative example 1
0.1g microcrystalline celluloses are placed in 2.0g 1- pi-allyl -3- methylimidazole chloride ion liquids, and it is molten in 100 DEG C
10min is solved, is added after 70 μ L water in 150 DEG C of heating 30min.Reaction solution is diluted with water and filtered, and filtrate is settled to 100mL, adopts
TRS is determined with DNS methods, and reaction product is analyzed using high performance liquid chromatography, it is 16.3% to measure TRS, and glucose is received
Rate is 5.4%.
Examples detailed above shows, using a kind of wood fibre based on support type perrhenate ions liquid catalyst of the present invention
Plain biodegrading process can make cellulose fully degrade, and obtain the glucose of higher yields.The catalytic process is avoided using traditional
Strong acid catalyst, course of reaction and catalyst lock out operation are simply easy, and one is provided newly for the Degradation and Transformation of lignocellulosic
Process route.
Claims (10)
1. a kind of cellulose degradation method based on support type perrhenate ions liquid, it is characterised in that comprise the following steps：
Take appropriate cellulose to be dissolved in ion liquid solvent, after 90~110 DEG C dissolve, add appropriate support type perrhenate ions liquid
Body catalyst, 10~60min is reacted at 120~170 DEG C, and reaction solution is diluted with water by reaction after terminating, and is filtered.
2. a kind of cellulose degradation method based on support type perrhenate ions liquid according to claim 1, it is special
Levy and be, described support type perrhenate ions liquid is：Structural formula as shown in (I) based on ReO4 -The support type of anion
Perrhenate ions liquid or structural formula as shown in (II) based on ReO4 -The support type sulfonic acid funtionalized perrhenate of anion
Ionic liquid or structural formula as shown in (III) based on ReO4 -The support type carboxylic acid functional perrhenate ions liquid of anion
Body；
Wherein, the integer of n=0~8.
3. a kind of cellulose degradation method based on support type perrhenate ions liquid according to claim 2, it is special
Levy and be：It is described based on ReO4 -The support type sulfonic acid funtionalized perrhenate ions liquid of anion is 1- (3- sulfonic acid) third
Base -3- methylimidazole perrhenate ions liquid；Preparation method comprises the following steps：By MCM-41 molecular sieves and the second of chloropropyl three
In TMOS addition organic solvent, in 20~200 DEG C of 1~24h of stirring, imidazoles is added, continues to stir 1~24h, filters, do
It is dry, obtain intermediate A；By intermediate A and 1,3- propane sultones are placed in organic solvent, 70 DEG C of back flow reaction 24h, cooling,
Filtering, and washed with ether, 8h is dried in vacuo at 50 DEG C, ionic liquid intermediate B is obtained；Add in a certain amount of organic solvent
Enter ionic liquid intermediate B and 37% concentrated hydrochloric acid, 12h is reacted at 70 DEG C, after reaction completely, filtering obtains intermediate C；
Intermediate C and ammonium perrhenate are added in organic solvent, 1~24h is stirred at room temperature, is filtered, and are dried, are obtained 1- (3- sulfonic acid) third
Base -3- methylimidazole perrhenate ions liquid.
4. a kind of cellulose degradation method based on support type perrhenate ions liquid according to claim 3, it is special
Levy and be：In molar ratio, chloropropyl triethoxysilane:MCM-41 molecular sieve=1:1~1:3rd, chloropropyl triethoxysilane:
Imidazoles=1:1~1:3rd, intermediate A:1,3- propane sultone=1:1~1:4th, intermediate B:Concentrated hydrochloric acid=1:1~1:2nd, in
Mesosome C:Ammonium perrhenate=1:1~1:1.5.
5. a kind of cellulose degradation method based on support type perrhenate ions liquid according to claim 2, it is special
Levy and be：It is described based on ReO4 -The support type carboxylic acid functional perrhenate ions liquid of anion is 1- (α-carboxylic acid) first
Base -3- methylimidazole perrhenate ions liquid；Preparation method comprises the following steps：By MCM-41 molecular sieves and the second of chloropropyl three
In TMOS addition organic solvent, in 20~200 DEG C of 1~24h of stirring, imidazoles is added, continues to stir 1~24h, filters, do
It is dry, obtain intermediate A；Intermediate A and ethyl chloroacetate are dissolved in organic solvent, 70 DEG C of back flow reaction 24h, cooled down, filtering, and
Washed with ether, 8h is dried in vacuo at 50 DEG C, obtain ionic liquid intermediate B；Add in organic solvent in the middle of ionic liquid
Body B and 37% concentrated hydrochloric acid, reacts 12h at 70 DEG C, cools down, filtering, and is washed with ether, is dried in vacuo, obtains intermediate
C；Intermediate C and ammonium perrhenate are added in organic solvent, 1~24h is stirred at room temperature, is filtered, and are dried, are obtained 1- (α-carboxylic acid)
Methyl -3- methylimidazole perrhenate ions liquid.
6. a kind of cellulose degradation method based on support type perrhenate ions liquid according to claim 5, it is special
Levy and be：In molar ratio, chloropropyl triethoxysilane:MCM-41 molecular sieve=1:1~1:3rd, chloropropyl triethoxysilane:
Imidazoles=1:1~1:3rd, intermediate A:Ethyl chloroacetate=1:1~1:4th, intermediate B:Concentrated hydrochloric acid=1:1~1:2nd, intermediate C:
Ammonium perrhenate=1:1~1:1.5.
7. a kind of cellulose degradation method based on support type perrhenate ions liquid according to claim 3 or 5, its
It is characterised by：Described organic solvent is ethanol, methanol, acetonitrile, toluene or ethyl acetate.
8. a kind of cellulose degradation method based on support type perrhenate ions liquid according to claim 1, it is special
Levy and be：Described ion liquid solvent is that anion is selected from Cl-、CH3COO-And RPO2 -, cation is selected from [Cnmim]+、
[R4N]+[Cnpy]+, n=1~8, R is methyl, ethyl, normal-butyl or n-hexadecyl.
9. a kind of cellulose degradation method based on support type perrhenate ions liquid according to claim 1, it is special
Levy and be：The mass ratio of cellulose and ion liquid solvent is 1:5~40, the addition based on support type perrhenate ions liquid
Measure as the 10%~100% of cellulose quality.
10. a kind of cellulose degradation method based on support type perrhenate ions liquid according to claim 1, it is special
Levy and be：Described cellulose is microcrystalline cellulose or lignocellulosic；Or cellulose origin is in straw and stalk.
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