CN106902877B - A kind of polyacid catalyst and preparation method thereof and application method - Google Patents
A kind of polyacid catalyst and preparation method thereof and application method Download PDFInfo
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- CN106902877B CN106902877B CN201610966044.9A CN201610966044A CN106902877B CN 106902877 B CN106902877 B CN 106902877B CN 201610966044 A CN201610966044 A CN 201610966044A CN 106902877 B CN106902877 B CN 106902877B
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- xylose
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 18
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims abstract description 24
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims abstract description 12
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 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 claims abstract description 10
- 239000008103 glucose Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 12
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 12
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 9
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 229920002522 Wood fibre Polymers 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- FVIZARNDLVOMSU-UHFFFAOYSA-N ginsenoside K Natural products C1CC(C2(CCC3C(C)(C)C(O)CCC3(C)C2CC2O)C)(C)C2C1C(C)(CCC=C(C)C)OC1OC(CO)C(O)C(O)C1O FVIZARNDLVOMSU-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 239000002304 perfume Substances 0.000 claims 1
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 229940015043 glyoxal Drugs 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 9
- 229960003487 xylose Drugs 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229920002488 Hemicellulose Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 229920005610 lignin Polymers 0.000 description 5
- 238000001907 polarising light microscopy Methods 0.000 description 5
- 229920006324 polyoxymethylene Polymers 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 150000002772 monosaccharides Chemical class 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000012978 lignocellulosic material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 1
- 241001464837 Viridiplantae Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical compound O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006400 oxidative hydrolysis reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002972 pentoses Chemical class 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000009923 sugaring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002916 wood waste Substances 0.000 description 1
Classifications
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/02—Monosaccharides
Abstract
The polyacid catalyst and preparation method thereof that the invention discloses a kind of to convert for being catalyzed lignocellulosic orientation, which is the polyacid compound with structure with Keggin, prepares glucose sugar, xylose and glyoxal with this catalyst lignocellulosic.Catalyst has high catalytic activity, repeatability and extensive adaptability to raw materials, and whole preparation process is generated without waste water, environmentally protective.
Description
Technical field
The present invention is catalyst preparation and applied technical field, and in particular to a kind of new nano-solid polyacid catalyst,
Simultaneously the invention further relates to the preparation of this nanocatalyst and its in the application of lignocellulosic orientation conversion aspect.
Background technique
The development of in the 21st century, modern society is faced with the serious problems such as shortage of resources, energy crisis and environmental degradation,
The shortage of fossil resource has become one of bottleneck factor of global economic development, therefore each state all proposes to develop war accordingly
Slightly.In order to protect the energy saving people of environment to concentrate on sight on renewable resource, biological material and the energy gradually emersion
The water surface, so that the development of Biomass Industry has become the important development strategy in China.Biomass is widely present on earth, it
It is to be formed by organic matter using the photosynthesis of green plants, mainly includes carbohydrate (such as monosaccharide, starch), stalk, wooden
Cellulose, grease etc., therefore, biomass are inexhaustible resource treasure-houses.
Wherein, lignocellulosic is the renewable resource that nature is widely present, and unedible lignocellulosic includes each
The careless class of kind, forestry industrial wood waste, agricultural wastes straw etc..China is large agricultural country, and lignocellulosic sources are very rich.
Wherein annual to generate about more than 200,000,000 tons of agricultural crop straw, stalk has become a kind of useless burden object, and stalk on-site incineration is increasingly
Seriously, the smog of generation becomes a great society public hazards.The main component of stalk is fiber, hemicellulose and lignin, by hydrolysis
Saccharification, cellulosic material can be converted into monosaccharide substance, as platform, on the one hand can be converted to fuel oil, combustion through chemistry route
Gas and chemicals；On the other hand large fermented product and liquid biofuel can be converted to by biocatalysis；Wherein utilize knot
The monosaccharide crystal that brilliant purification technique obtains more is important the raw material of industry.Lignocellulosic material sugaring (including glucose and wood
Sugar) technology is the key that agricultural crop straw using chemicals is prepared, it is the key that subsequent transformation and Steps.
At present the preprocess method that uses in the world mainly have physical method (thermal degradation, radiation degradation and mechanical degradation),
Biological method (microorganism) and chemical method (oxidation and hydrolysis).Physical method simple process, it is easily operated, but its catabolite
Complexity, target product is difficult to control and poor selectivity.Microbial method reaction condition is mild, environmental-friendly, selectivity is high, equipment letter
It is single, with the development of modern biotechnology investigative technique, have become the hot spot of current research.But high production cost, preparation purification are tired
Difficult, catalytic activity and stability is all lower, the reaction time is long, and preprocessing process is complicated, is still difficult to realize so far extensive
Industrial application.Chemical method includes oxidative degradation and hydrolysis.Traditional inorganic acid such as H2SO4Pretreatment is now widely used pre-
Processing method, under high temperature (170-240 DEG C) and condition of high voltage, it can discharge most of pentose, and can improve cellulose
Hydrolysis effect.But hemicellulose resolves into xylose with this condition, and xylose non-refractory high pressure continues degradation and forms fermentation suppression
Object furfural processed；Single treatment is lower to the removal rate of lignin simultaneously, within 20%；It is a large amount of that product needs depickling processing to generate
Waste water.The problems such as causing high energy consumption, equipment burn into complex process, a large amount of spent acid and environmental pollution, it has also become constraints on fiber element rule
The technical bottleneck of modelling production.NaOH, KOH alkalescence pretreatment are poly- in non-degradable hemicellulose compared with acid and other oxidants
In the case where zoarium, it is more advantageous to the ester bond broken between lignin, hemicellulose and cellulose, but higher cost and dealkalize
Processing limits the large-scale use of this method.Oxidation pre-treatment is using wet oxidation (Wetoxidation) technology in high temperature
Lignocellulosic material is aoxidized in the presence of water vapour and high pressure oxygen are common, keeps partial lignin and most of hemicelluloses molten
Solution, but still there is high consumption and the high cost problem of equipment.
Polyoxometallate (POMs, also referred to as polyacid HPAs), while having goodAcid and oxidation
Reproducibility is a kind of acid and oxidation reduction catalyst for having major application in the industry.Compared with traditional catalyst sulfuric acid etc.,
Have the characteristics that nontoxic, free of contamination, is environmental type solid acid type and oxidation catalyst.In numerous POMs, Keggin
Type titaniferous polyacid H3+2x[PW12-xTixO40] (x=1-3) be applied in oxidation reaction, have good catalysis oxidation ability and
Certain acid energy, uses in numerous organic reactions.Use in catalysis lignocellulosic orientation conversion, currently without
Report.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of for being catalyzed the polyacid of lignocellulosic orientation conversion
Catalyst and preparation method thereof, and application method of the polyacid catalyst in lignocellulosic orientation conversion.
The present invention solve technical problem the technical solution adopted is that:
A kind of polyacid catalyst converted for being catalyzed lignocellulosic orientation, is the polyacid chemical combination with structure with Keggin
Object, the general formula of the polyacid compound are as follows:
[C16H33N(CH3)3]3+2x[PW12-xTixO40] (x=1,2,3)
A kind of polyacid catalyst converted for being catalyzed lignocellulosic orientation, preparation method are as follows:
1:0-5 weighs polyacid compound K respectively in molar ratio3+2x[PW12-xTixO40]·6H2O and surfactant
[C16H33(CH3)3N]Br；Polyacid compound K3+2x[PW12-xTixO40]·6H2O is poured into reactor, and it is 1 that mass ratio, which is added:
5-10 times of distilled water is heated to 50-70 DEG C, stirring and dissolving；Surfactant is added thereto again, it is small that reaction solution is aged 5-10
When, white solid object is precipitated, filtering is precipitated 2-3 times with distilled water flushing, until the pH value of eluate reaches 5-8, is precipitated
Object；The sediment is placed in Muffle furnace, is converted in 150-300 DEG C to get to a kind of lignocellulosic orientation within sintering 2-6 hours
Polyacid catalyst.
A kind of application method of polyacid catalyst in lignocellulosic orientation conversion is as follows:
Lignocellulosic, catalyst, water are added in high-pressure reactor according to a certain percentage (1:4.5:70), setting is anti-
Answer 80~140 DEG C of temperature, the reaction time 5~10 hours, so that lignocellulosic is converted into glucose, xylose and vanillic aldehyde.It urges
10~50mg of dosage of agent.After reaction, it is centrifugated out catalyst and unreacted wood fibre, repeats to convert.It produces
Object is extracted twice with methyl iso-butyl ketone (MIBK), and 40 DEG C of organic phase steam methyl iso-butyl ketone (MIBK), obtains product vanillic aldehyde；Water
It is mutually extracted with ethyl alcohol, 40 DEG C of ethyl alcohol phase steam ethyl alcohol and obtain glucose；50 DEG C of remaining water phase steams water
Obtain xylose.
The beneficial effects of the present invention are:
Many technologies can be solved in lignocellulosic orientation process using the polyacid of structure with Keggin as catalyst
Property problem:
1, the polyacid of structure with Keggin contains Ti and W, has high oxidative capacity, simultaneously because urging there are the acid site Lewis
Agent has certain acid energy, can satisfy the need of the dual pretreatment separating lignin of acid/oxidation, cellulose and hemicellulose
It wants, realizes that wood fibre orientation is converted into glucose, xylose and vanillic aldehyde；
2, POMs system is the solid catalyst at the dual center of acid/oxidation.It is non-equal in lignocellulosic reaction system
Phase catalyst is easy to separate from reaction system, and regeneration method is easy, does not generate large amount of sewage, reduce catalyst use at
This.
3, POMs solid catalyst is self-assembly of " nanometer system " in aqueous systems, improves the specific surface area of catalyst,
To improve the catalytic activity of catalyst.Catalyst high conversion efficiency.
4, POMs one-step method handles lignocellulosic, easy to operate, does not need the separation process of intermediate product, preparation cost
It is low, and the secondary pollution of green, anaerobic agent.
The polyacid catalyst that different compositions are synthesized by design can satisfy lignocellulosic orientation conversion and prepare grape
The needs of sugar, xylose and vanillic aldehyde, it is practical.
Specific embodiment
Embodiment one
Molar ratio 1:4 polyacid compound K is weighed respectively5[PW11TiO40]·6H2O and surfactant [C16H33(CH3)3N]
Br；Polyacid compound K5[PW11TiO40]6H2O is poured into reactor, and the distilled water that mass ratio is 6 times is added, is heated to 60
DEG C, stirring and dissolving；Surfactant is added thereto again, reaction solution is aged 7 hours, and white solid object, filtering, with distillation is precipitated
Water rinses precipitating 3 times, until the pH value of eluate reaches 7.1, obtains sediment；The sediment is placed in Muffle furnace, in 170
DEG C sintering 2 hours to get to a kind of lignocellulosic orientation conversion polyacid catalyst, yield 50%.
Embodiment two
By lignocellulosic 1g, 30mg [C16H33(CH3)3N]5[PW11TiO40]·6H2The catalyst of O is put into reaction under high pressure
In device, the deionized water of 6mL, heating stirring is added.Reaction temperature is 100 DEG C, and the reaction time is 8 hours.After reaction, cold
But reaction mixture is put into centrifuge tube afterwards and is centrifuged, included product glucose, xylose and vanillic aldehyde in clear liquid, sink
It is responseless lignocellulosic and catalyst in shallow lake.Product is extracted twice with methyl iso-butyl ketone (MIBK), 40 DEG C of organic phase decompressions
Methyl iso-butyl ketone (MIBK) is steamed, product vanillic aldehyde is obtained；Water phase is extracted with ethyl alcohol, and 40 DEG C of ethyl alcohol phase steam ethyl alcohol
Obtain glucose；50 DEG C of remaining water phase steams water and obtains xylose；Yield is respectively 45%, 30% and 61%.
Claims (2)
1. it is a kind of for being catalyzed the polyacid catalyst of lignocellulosic orientation conversion,
The polyacid catalyst is the polyacid compound with structure with Keggin, the general formula of the polyacid compound are as follows:
[C16H33N(CH3)3]3+2x[PW12-xTixO40], wherein x=1,2,3；Preparation method is as follows:
1:0-5 weighs polyacid compound K respectively in molar ratio3+2x[PW12-xTixO40]·6H2O and surfactant [C16H33
(CH3)3N] Br, wherein the mole of surfactant does not take 0；Polyacid compound K3+2x[PW12-xTixO40]·6H2O is poured into
In reactor, the distilled water that mass ratio is 1:5-10 times is added, is heated to 50-70 DEG C, stirring and dissolving；Surface is added thereto again
Activating agent, reaction solution are aged 5-10 hours, and white solid object is precipitated, and filtering is precipitated 2-3 times with distilled water flushing, until washing out
The pH value of liquid reaches 5-8, obtains sediment；The sediment is placed in Muffle furnace, in 150-300 DEG C sintering 2-6 hours, obtain
Polyacid catalyst is converted into glucose, xylose and vanillic aldehyde for being catalyzed lignocellulosic orientation.
2. a kind of application method of the polyacid catalyst described in claim 1 in lignocellulosic orientation conversion, it is characterised in that:
Lignocellulosic, polyacid catalyst described in claim 1 and water are added to high pressure according to mass ratio 1:4.5:70
In reactor, 80~140 DEG C of reaction temperature, the reaction time 5~10 hours, make lignocellulosic be converted into glucose, xylose and
Vanillic aldehyde, 10~50mg of catalyst amount；After reaction, it is centrifugated out catalyst and unreacted wood fibre, is repeated
Conversion；Product is extracted twice with methyl iso-butyl ketone (MIBK), and 40 DEG C of organic phase steam methyl iso-butyl ketone (MIBK), obtains product perfume
Oxalaldehyde；Water phase is extracted with ethyl alcohol, and 40 DEG C of ethyl alcohol phase steam ethyl alcohol and obtain glucose；50 DEG C of remaining water phase vacuum distillations
It steams water and obtains xylose.
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| CN108689819B (en) * | 2018-05-24 | 2021-03-30 | 中国石油大学(华东) | Novel method for degrading wood chips through catalytic oxidation of polyoxometallate |
| CN109499612B (en) * | 2018-12-17 | 2021-09-17 | 东北师范大学 | Polyacid catalyst and preparation method and application thereof |
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