CN110028397A - A kind of application of the polyacid catalyst of the structure containing Dawson in cellulose hydrothermal conversion - Google Patents
A kind of application of the polyacid catalyst of the structure containing Dawson in cellulose hydrothermal conversion Download PDFInfo
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- CN110028397A CN110028397A CN201910409108.9A CN201910409108A CN110028397A CN 110028397 A CN110028397 A CN 110028397A CN 201910409108 A CN201910409108 A CN 201910409108A CN 110028397 A CN110028397 A CN 110028397A
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- catalyst
- cellulose
- acid
- lactic acid
- hydrothermal conversion
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- 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
- B01J27/19—Molybdenum
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- Organic Chemistry (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention relates to a kind of methods applied to cellulose hydrothermal conversion, contain simultaneouslyThe Dawson structure polyacid catalyst of acid and Lewis acid prepares the purposes of lactic acid in cellulose hydrothermal conversion.Catalyst is the Dawson structure polyacid composite catalyst Ag of silver displacementxH6‑xP2Mo18O62(x=1~6) are used in cellulose hydrothermal conversion, its orientation may be implemented and be converted into lactic acid.Catalyst has high activity, and cellulose substantially completely converts, and the yield of lactic acid reaches 57.8%, and has good reusing.Whole process does not have waste water, exhaust gas to generate, environmentally protective.
Description
Technical field
The present invention is catalyst applied technical field, is contained with one kind is related toAcid is with Lewis acid and properly
The Dawson type polyacid catalyst of oxidation-reduction quality the application of lactic acid is prepared in cellulose hydrothermal conversion.
Technical background:
Fossil fuel resource rapid exhausted and it has caused great concern in the whole world to the adverse effect of environment.
It therefore the use of fossil fuel and related petrochemical is not long-term plan, urgent need seeks a kind of sustainable alternative.Mesh
Before, fuel (biodiesel, bio-ethanol and biogas), chemicals (acetic acid, malic acid, third are produced using biomass as raw material
Ketone, lactic acid) and material be considered as the key for ensuring the following low-carbon economy, have potential economy, environmental and social benefits:
Benefit in terms of economy and society is mainly increased and competitiveness and subtracted with the new investment of supporting industry department, reinforced region
It is few related to the dependence of fossil fuel.The most important sustainable use for haveing an advantage that carbon, closed carbon cycle in terms of environment
Journey not will increase the gas concentration lwevel in atmosphere.
The utilization of biomass energy mainly passes through the conversion processes such as pyrolysis, hydrolysis/alcoholysis, hydrothermal liquefaction, gasification, charing
It realizes.Cellulose is often used as the primary research object of biomass conversion as biomass the most abundant on the earth.Wherein
After hydrothermal conversion occurs for cellulose, available kinds of platform compound.These plateform molecules have very extensive purposes, can answer
For chemicals, material, the energy etc..In cellulose conversion processes, reaction process is divided into two steps: the first step is
Cellulose is hydrolyzed into water-soluble sugar, including oligomer and glucose.The step is mainly concerned with the activation of C-O glycosidic bond.Second
Step is that glucose passes through the series reactions such as isomerization, hydrogenolysis, oxidation generation sugar alcohol and organic acid, therefore some important platforms
Compound, such as ethylene glycol, propylene glycol, lactic acid carbon atom are less than 6 compounds, can directly be produced by cellulose.
Lactic acid mainly forms (~90%) by carbohydrate fermentations such as sugar, sucrose.However, there are space-time yields for the technique
Low, enzyme price is high, bad bisulfate waste liquor, the problems such as purification difficulty is big.In addition, this biocatalysis process is only limitted to monosaccharide or disaccharides
Conversion.Therefore more and more research work are dedicated to developing the life richer from glucose or cellulose and hemicellulose etc.
The chemical catalysis system of lactic acid or lactic acid is produced in physical resources.And realize that the effective ways of this target are using in more activity
The catalyst of the heart could be completed.
Polyacid has many applications as acid catalyst and oxidation-reduction catalyst in biomass energy conversion, but mostly living
Application study of the catalyst that property center is integrated in compound tandem reaction is less.Using simultaneously have containingAcid
With the Dawson type polyacid catalyst Ag of Lewis acid and suitable oxidation-reduction qualityxH6-xP2Mo18O62Turn in cellulose hydro-thermal
Change prepare lactic acid application in solve many technical problems:
1.AgxH6-xP2Mo18O62'sAcid and Lewis acid and high total acidity and redox property can lead to
The introducing for crossing Ag is adjusted, and meets cellulose hydro-thermal orientation and converts and improve the yield of lactic acid.
2. by using Ag+After the proton formation insoluble salt for exchanging polyacid, enhancing catalyst Lewis is acid, is more advantageous to
The generation of lactic acid.The specific surface area of catalyst also greatly increases simultaneously, makes reactant be easier to be enriched to active site, overcomes biography
Matter obstacle.
3. catalyst has high activity, low cost, stabilization, water-fast and heterogeneous etc. advantages, reusable.
Summary of the invention
The present invention, which provides one kind, to be hadThe Ag of acid and Lewis acid and redox propertyxH6-xP2Mo18O62Catalysis
Agent is prepared in lactic acid for cellulose hydrothermal conversion.For this purpose, it is practiced by following scheme:
A kind of solid catalyst is prepared with following method:
By H6P2Mo18O62It is dissolved in 20~50mL deionized water.Under conditions of being vigorously stirred at room temperature, thereto
The AgNO of appropriate concentration is added dropwise320~50mL of solution (H6P2Mo18O62And AgNO3Molar ratio 1:1~6).Obtained mixture is existed
It is aged 2h at room temperature, filters, washs, it is dry.6h is calcined in 200 DEG C of still air obtains pale yellow powder.It generates
AgxH6-xP2Mo18O62, yield reaches 60~80%.
With the present invention provides a kind of celluloses to prepare lactic acid polyacid catalyst, the method is as follows:
In a high pressure reaction kettle, the cellulose and 50~100mgAg of 10~50mg is addedxH6-xP2Mo18O62Catalyst.It will
When mixed liquor is heated to 120~160 DEG C, reaction carries out 9~13h.After reaction, catalyst is centrifugated reuse.Product
It is examined with ion chromatography, the conversion ratio of cellulose and the yield of lactic acid can achieve 84~100% and 34.5~57.8% respectively.
Specific embodiment
Embodiment 1
By H6P2Mo18O62It is dissolved in 20mL deionized water.Under conditions of being vigorously stirred at room temperature, it is added dropwise thereto
The AgNO of appropriate concentration330mL solution (H6P2Mo18O62And AgNO3Molar ratio 1:2).Obtained mixture is aged at room temperature
2h is filtered, and is washed, dry.6h is calcined in 200 DEG C of still air obtains pale yellow powder.Generate Ag2H4P2Mo18O62,
Yield reaches 71%.
Embodiment 2
In a high pressure reaction kettle, it is added and contains 10mg cellulose, while 80mgAg is added2H4P2Mo18O62Composite catalyst,
When this mixture is heated to 150 DEG C, reaction carries out 13h.After reaction, catalyst centrifuge separation is used for next time anti-
It answers.Product is examined with ion chromatography, and the conversion ratio of cellulose reaches 100%, and the yield of lactic acid reaches 57.8%.
Claims (2)
1. a kind of catalyst for preparing lactic acid for cellulose hydrothermal conversion, feature containAcid and Lewis acid and conjunction
Suitable oxidation-reduction quality guarantees that cellulose hydrothermal conversion prepares lactic acid, has following general formula:
AgxH6-xP2Mo18O62(x=1~6).
2. a kind of containing for catalytic cellulose as described in claim 1Acid and Lewis acid and suitable oxygen
Change the Dawson type polyacid catalyst of reduced form, the compound is preferred are as follows:
(1)AgH5P2Mo18O62
(2)Ag2H4P2Mo18O62
(3)Ag3H3P2Mo18O62
(4)Ag4H2P2Mo18O62
(5)Ag5HP2Mo18O62
(6)Ag6P2Mo18O62。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910409108.9A CN110028397A (en) | 2019-05-15 | 2019-05-15 | A kind of application of the polyacid catalyst of the structure containing Dawson in cellulose hydrothermal conversion |
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| CN201910409108.9A CN110028397A (en) | 2019-05-15 | 2019-05-15 | A kind of application of the polyacid catalyst of the structure containing Dawson in cellulose hydrothermal conversion |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058852A (en) * | 2013-01-25 | 2013-04-24 | 陕西师范大学 | Method for preparing lactic acid by hydrolyzing biomass |
| CN105080608A (en) * | 2014-05-06 | 2015-11-25 | 东北师范大学 | Application of novel polyacid catalyst in cellulose hydrolyzation |
| CN107088438A (en) * | 2017-05-04 | 2017-08-25 | 东北师范大学 | The method for preparing lactic acid with the selective conversion of catalyzing glycerol containing molybdenum heteropolyacid |
| CN108772100A (en) * | 2018-05-22 | 2018-11-09 | 广东工业大学 | A kind of heteropolyacid salt solid catalyst and its preparation method and application |
-
2019
- 2019-05-15 CN CN201910409108.9A patent/CN110028397A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058852A (en) * | 2013-01-25 | 2013-04-24 | 陕西师范大学 | Method for preparing lactic acid by hydrolyzing biomass |
| CN105080608A (en) * | 2014-05-06 | 2015-11-25 | 东北师范大学 | Application of novel polyacid catalyst in cellulose hydrolyzation |
| CN107088438A (en) * | 2017-05-04 | 2017-08-25 | 东北师范大学 | The method for preparing lactic acid with the selective conversion of catalyzing glycerol containing molybdenum heteropolyacid |
| CN108772100A (en) * | 2018-05-22 | 2018-11-09 | 广东工业大学 | A kind of heteropolyacid salt solid catalyst and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| DEVELOPMENT OF GA SALT OF MOLYBDOPHOSPHORIC ACID FOR BIOMASS CON: "Development of Ga salt of molybdophosphoric acid for biomass conversion to levulinic acid", 《ENERGY & FUELS》 * |
| FLORA CHAMBON等: "Cellulose hydrothermal conversion promoted by heterogeneous Brønsted and Lewis acids: Remarkable efficiency of solid Lewis acids to produce lactic acid", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| WANG ENBO等: "Preparation and Characterization of Heteropoly Octadecamolybdodiphosphates", 《CHEMICAL RESEARCH IN CHINESE UNIVERSITIES》 * |
| 张鑫宁: "Dawson型多金属氧酸盐的合成及其在催化纤维素水热转化中的性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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