CN110026217A - A kind of application of more molybdic acid catalyst of argentiferous in oxycellulose - Google Patents
A kind of application of more molybdic acid catalyst of argentiferous in oxycellulose Download PDFInfo
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- CN110026217A CN110026217A CN201910316024.0A CN201910316024A CN110026217A CN 110026217 A CN110026217 A CN 110026217A CN 201910316024 A CN201910316024 A CN 201910316024A CN 110026217 A CN110026217 A CN 110026217A
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- Prior art keywords
- acid
- catalyst
- oxycellulose
- pmo
- lactic acid
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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
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of methods applied to oxycellulose, contain simultaneouslyAcid combines the purposes for preparing lactic acid and formic acid with more molybdic acid catalyst of Lewis acid in oxycellulose.Catalyst is more molybdic acid composite catalyst Ag of the structure with Keggin of silver displacementxH3‑xPMo12O40(x=1~3) are used for cellulose oxidation reaction, its orientation may be implemented and be converted into lactic acid and formic acid.Catalyst has the selectivity and reusable property of high cellulose conversion ratio and product.Whole process does not have waste water, exhaust gas to generate, environmentally protective.
Description
Technical field
The present invention is the applied technical field of polyacid catalyst, and the more molybdic acid catalyst for being related to a kind of novel argentiferous are aoxidizing
Application in terms of cellulose.
Technical background
With fossil fuel increasingly consume with the continuous deterioration of environment, biomass energy is as a kind of cleaning and reproducible
The energy is the desirable feedstock that unique alternative fossil energy is converted into industrial chemicals or fuel, the attention by various countries.According to estimating
Meter, the whole world is every year by the fixed carbon of photosynthesis up to 2 × 1011Ton, energy content 3 × 1018Kilojoule can be used for developing
The energy be about as much as whole world year consumption ten times of energy, the potentiality of development and utilization are quite huge.Huge biomass benefit
Key is its effective chemistry, bioconversion, in particular how chemically direct it be converted into it is some high additional
The biological platform chemicals of value.Realize this purpose, designing novel, green, efficient, mild chemical new process is environmental resource
The key utilized.
Cellulose is a kind of natural high-molecular compound, is the highest carbon resource of content in biomass, is used as reserves
Abundant, renewable, the sustainable natural resources recycled are the great plateform molecules raw materials for having biological value.Cellulose is
Linear polymer made of being connected by cyclic annular D-Glucose by β-Isosorbide-5-Nitrae-glycosidic bond, meanwhile, in the macromolecule knot of cellulose
In structure unit, the hydrogen bond also formed containing a large amount of glycosidic bond and hydroxyl keeps its structural stability fine, it is difficult to destroy.And
Solubility is very low in water for cellulose, so being difficult to degrade.Therefore, how the efficient oxidation cellulose degradation obtains high chemical values
Product is important prerequisite and key that biomass energy is develop and useedd.Meanwhile cellulolytic activity component is more and complicated, oxidation turns
Change by-product is more, and how selective oxidation is the critical issue with realistic meaning.
It is a kind of important industrial products that lactic acid, which is also known as Lactic acid, is widely applied in food, cosmetics and pharmacy
Field, and the important source material for producing polylactic acid.Polylactic acid is that a kind of biodegradable, environment amenable novel have
Machine polymer can be applied to the multiple fields such as fiber packing, medical instrument, delivery system.The side of traditional mode of production lactic acid
Method be using lactic acid bacteria by from starch sugar fermentation be made, the pH in fermentation process need to be maintained in the range of 5~7.It is this
Method working condition is more harsh, and yield is relatively low.Therefore, it develops new production technology and lactic acid is efficiently prepared by cellulose,
It is of great significance.
Heteropoly acid (HPAs) is a kind of strong inorganic solid acid, by transition metal as V, Mo, W etc. are formed by connecting by oxygen
Multi-metal oxygen cluster compound.Polyacid has regulatableAcid and Lewis acidity and oxidation-reduction quality, it is wide
It is general to be applied in many catalysis reaction and show good catalytic performance, show good prospects for commercial application.Report at present
Heteropoly acid cellulose oxidation reaction in mainly use the polyacid PMo containing vanadium, molybdenum12-nVnO40And H3PMo12O40.With
H3PMo12O40It compares, AgxH3-xPMo12O40It is pureLewis metal ion Ag, Lewis acidic site is introduced in acid
Point can promote cellulose orientation to be converted into lactic acid.The original oxidation of polyacid is enhanced also using Lewis metal ion simultaneously
Proper energy power improves cellulose oxidation reaction speed.
It can be solved during oxycellulose is converted into lactic acid and formic acid using more molybdic acids of argentiferous as catalyst
Certainly many technical problems:
1. silver medal partly or entirely replaces the proton in polyacid and the polyacid catalyst (Ag for preparingxH3-xPMo12O40) have simultaneously
HaveThe acid oxidation-reduction quality with Lewis acidity and raising, can satisfy the needs of oxycellulose.
2.AgxH3-xPMo12O40It is a kind of solid catalyst, can be used as a kind of heterogeneous catalysis recycling, green nothing
Economic cost is saved in pollution.
3.AgxH3-xPMo12O40Adjustable different silver-colored displacement number includes acid, acid to reach regulation catalyst activity
Distribution and redox property realize the reaction process of regulation oxycellulose and the selectivity of product.
Summary of the invention
The present invention provides a kind of while havingAcid and Lewis acidity and oxidation-reduction quality polyacid catalyst
AgxH3-xPMo12O40, lactic acid and formic acid are prepared for oxycellulose.For this purpose, implemented using following scheme.
A kind of solid catalyst preparation method:
1:1-3 weighs polyacid compound H respectively in molar ratio3PMo12O40And AgNO3.Respectively by polyacid compound
H3PMo12O40And AgNO3It is dissolved in the distilled water that mass ratio is respectively 1:10~100 and 1:10~50, by AgNO3In solution
H is instilled dropwise3PMo12O40In solution, stir 1~8h at room temperature, solid be precipitated, by the method for vacuum filtration separate solid with
Solution obtains yellow solid, is washed with distilled water 2-3 times, 8 hours dry at 50 DEG C.Obtained solid is placed in Muffle furnace again
In the 2-6h hours removing crystallizations water of 250 DEG C of calcinings.It is prepared that a kind of oxycellulose prepares lactic acid and the polyacid of formic acid is urged
Agent.Its yield is 80%.
With a kind of polyacid catalyst for preparing lactic acid and formic acid provided by the invention, catalysis oxidation cellulose prepare lactic acid and
The method of formic acid is as follows:
Cellulose, catalyst and water is taken to be put into pyroreaction kettle according to a certain percentage (1:0.01~0.5:30~100)
In, reaction temperature is set as 130 DEG C~170 DEG C, and revolving speed 800rpm is passed through 0.1~1MPa after reaction kettle reaches target temperature
Oxygen, stable gas pressure start timing.Reaction time is 5~9h.Mixture is cooled down after reaction, is urged by being centrifugated solid
The conversion ratio of agent and unreacted cellulose, cellulose reaches 90% or more.Product lactic acid and formic acid use high-effect ionic color
Spectrum carries out analysis detection, and yield respectively reaches 50% and 30%.
Embodiment 1
1:1 weighs polyacid compound H respectively in molar ratio3PMo12O40And AgNO3.Respectively by polyacid compound
H3PMo12O40And AgNO3It is dissolved in the distilled water that mass ratio is respectively 1:100 and 1:10, by AgNO3It is instilled dropwise in solution
H3PMo12O40In solution, 4h is stirred at room temperature, solid is precipitated, and solid and solution are separated by the method for vacuum filtration, obtain Huang
Color solid is washed with distilled water 3 times, 8 hours dry at 50 DEG C.Obtained solid is placed in 250 DEG C of calcining 4h in Muffle furnace again
Hour removes the crystallization water.The polyacid catalyst that a kind of oxycellulose prepares lactic acid and formic acid is prepared.Its yield is
80%.
Embodiment 2
It weighs 0.1g cellulose and 10wt% catalyst is put into pyroreaction kettle, 6mL distilled water is added, reaction temperature is set
It is set to 150 DEG C, revolving speed 800rpm, oxygen 1MPa is passed through after reaction kettle reaches target temperature, stable gas pressure starts timing.Instead
It is 8 hours between seasonable.Mixture is cooled down after reaction, it is fine by centrifuge separation solid catalyst and unreacted cellulose
The conversion ratio of dimension element reaches 90%.Using high-efficient ion chromatogram progress analysis detection, yield is respectively reached for product lactic acid and formic acid
50% and 31%.
Claims (2)
1. a kind of polyacid catalyst for preparing lactic acid and formic acid for oxycellulose, the general formula of the catalyst are as follows:
AgxH3-xPMo12O40, wherein x=1~3.
2. the polyacid catalyst of lactic acid and formic acid, the polyacid are prepared for oxycellulose as claimed in claim 1
Catalyst are as follows:
Ag1H2PMo12O40,
Ag2H1PMo12O40,
Ag3PMo12O40。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910316024.0A CN110026217A (en) | 2019-04-19 | 2019-04-19 | A kind of application of more molybdic acid catalyst of argentiferous in oxycellulose |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910316024.0A CN110026217A (en) | 2019-04-19 | 2019-04-19 | A kind of application of more molybdic acid catalyst of argentiferous in oxycellulose |
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| CN110026217A true CN110026217A (en) | 2019-07-19 |
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| CN201910316024.0A Pending CN110026217A (en) | 2019-04-19 | 2019-04-19 | A kind of application of more molybdic acid catalyst of argentiferous in oxycellulose |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112371185A (en) * | 2020-12-04 | 2021-02-19 | 北华大学 | Polyacid catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PT101857A (en) * | 1996-03-27 | 1997-10-31 | Evtiouguine Prof Dr Dmitri | Process for the oxidative delignification of lignocellulose materials in the presence of heteropolyanions |
| CN108863784A (en) * | 2018-07-21 | 2018-11-23 | 东北师范大学 | Indoor temperature solid phase method synthesis HPAs nanocatalyst catalysis prepares Green Lubricants tricarboxymethyl propane oleate technology |
| CN109433266A (en) * | 2018-11-29 | 2019-03-08 | 东北师范大学 | Three center POMs catalysis oxidation glycerol of polylysine modification prepare the technology of lactic acid |
-
2019
- 2019-04-19 CN CN201910316024.0A patent/CN110026217A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PT101857A (en) * | 1996-03-27 | 1997-10-31 | Evtiouguine Prof Dr Dmitri | Process for the oxidative delignification of lignocellulose materials in the presence of heteropolyanions |
| CN108863784A (en) * | 2018-07-21 | 2018-11-23 | 东北师范大学 | Indoor temperature solid phase method synthesis HPAs nanocatalyst catalysis prepares Green Lubricants tricarboxymethyl propane oleate technology |
| CN109433266A (en) * | 2018-11-29 | 2019-03-08 | 东北师范大学 | Three center POMs catalysis oxidation glycerol of polylysine modification prepare the technology of lactic acid |
Non-Patent Citations (3)
| Title |
|---|
| ABAYNEH GETACHEW DEMESA ET AL.: "Valorization of Lignin by PartialWet Oxidation Using Sustainable Heteropoly Acid Catalysts", 《MOLECULES》 * |
| MEILIN TAO ET AL.: "Lewis-acid-promoted catalytic cascade conversion of glycerol to lactic acid by polyoxometalates", 《CHEMICAL COMMUNICATIONS》 * |
| MOHAMED MOKHTAR ET AL.: "Ethanol to hydrocarbons using silver substituted polyoxometalates: Physicochemical and catalytic study", 《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112371185A (en) * | 2020-12-04 | 2021-02-19 | 北华大学 | Polyacid catalyst and preparation method and application thereof |
| CN112371185B (en) * | 2020-12-04 | 2023-05-09 | 北华大学 | Polyacid catalyst and preparation method and application thereof |
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Application publication date: 20190719 |