CN102641746A - Heteropolyacid modified catalyst, and preparation and catalyst catalytic hydrolysis reaction system thereof - Google Patents
Heteropolyacid modified catalyst, and preparation and catalyst catalytic hydrolysis reaction system thereof Download PDFInfo
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- CN102641746A CN102641746A CN2012100977972A CN201210097797A CN102641746A CN 102641746 A CN102641746 A CN 102641746A CN 2012100977972 A CN2012100977972 A CN 2012100977972A CN 201210097797 A CN201210097797 A CN 201210097797A CN 102641746 A CN102641746 A CN 102641746A
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- heteropoly acid
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- acid modified
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention belongs to the technical field of the chemical industry and in particular relates to a heteropolyacid modified catalyst, and preparation and a catalyst catalytic hydrolysis reaction system thereof. The heteropolyacid modified catalyst contains heteropolyacid and an amine substance mixed together in a mol ratio of 1:(0.5-5). The heteropolyacid modified catalyst obtained in the invention is high in catalysis efficiency, and easy to be separated and recycled, and thus the catalyst has good industrial application prospect.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of heteropoly acid modified catalyst and preparation thereof and catalyst hydrolysis reaction system particularly.
Background technology
Current, inorganic acid is widely used in industrialization such as esterification, isomerization, hydrolysis reaction, though they have very high catalytic activity, has serious corrosivity, and toxicity is difficult to separate problems such as purification.Develop a kind of course of reaction green non-pollution, be easy to reclaim, and have highly active catalyst and become a kind of trend.Because of solid acid has highly acid, avirulence, high activity under the cryogenic conditions, and advantage such as be easy to reclaim, can be recycled and cause that day by day people pay close attention to.And heteropoly acid industrial applications aspect a lot, and it has strong B acid and presents highly acid, is a kind of desirable solid acid catalyst.
At present, there is big quantity research to report that heteropoly acid has been widely used in refining oil and the synthetic aspect of fine chemicals.(Li Shumian, Li Zhancai, Jiang Ling such as Li Shumian; Deng. heteropoly acid catalysis tetrahydrofuran ring opening polymerization reaction [J]. chemical research and application, 2003,15 (1): 48-50) with phosphato-molybdic heteropolyacid make catalyst, epoxychloropropane is that promoter, water or ethylene glycol are chain regulator; The optimum process condition that tetrahydrofuran ring opening polymerization prepares equal polyethers is: 0-2 ℃; Reaction 4h, productive rate reaches 64.5%, and molecular weight is in 2000.Suitable with the import properties of sample with its polyurethane elastomeric materials that makes, some performance is superior to the resin that imported raw material is processed.Zhuo Runsheng etc. (Zhuo Runsheng, Zhou Shixin, Tian Laijin, etc. with the heteropoly acid is the research [J] of catalyst synthesizing glycol one ether. Speciality Petrochemicals, and 1995,4:49-52) to PW
12Catalysis absolute ethyl alcohol and oxirane prepare the etherification reaction of ethanol ether to be studied, and has inquired into the mechanism of action of heteropoly acid catalysis etherification reaction.They compare with the experimental result of making catalyst with sulfuric acid, and the result finds that their catalytic activity is all higher, shows phenotype H
+Etherification is remarkable.When using Na
2S0
4When making catalyst, catalytically inactive almost. and use Na
3PO
4W
12XH
2When O made catalyst, its etherification activity was 20% of its acid.Liu Xiaoping etc. (Liu Xiaoping. the normal butane isomerization research [J] on the carried heteropoly acid catalyst. the gas chemical industry; 2002; 27 (3): 17-20) carried heteropoly acid catalyst has been carried out result of study to the isomerization reaction performance of normal butane and shown; The bifunctional catalyst of a kind of year Pt (mass fraction) 0.2% PW/ active carbon can make the isomerization selectivity of normal butane reach more than 85%, and conversion ratio reaches more than 23%.
Yet still there is the difficult problem that reclaims in heteropoly acid.At present, there is the scholar to attempt adopting ion modification (Cs
+, NH
4 +) method of heteropoly acid makes it easy to reclaim.Yet these methods all do not obtain better effects, address these problems extremely urgent so develop a kind of efficient and heteropoly acid catalysis system that be easy to reclaim.
Summary of the invention
The object of the invention is to provide a kind of heteropoly acid modified catalyst and preparation and catalyst hydrolysis reaction system.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is:
A kind of heteropoly acid modified catalyst, heteropoly acid modified catalyst are in molar ratio 1: heteropoly acid and amine substance that 0.5-5 mixes.
Said heteropoly acid modified catalyst then adds in the liquid medium for heteropoly acid and amine substance are mixed in the water-soluble or organic solvent under stirring condition, and precipitate is the heteropoly acid modified catalyst.
Said amine substance is a sulfamic acid, ethylenediamine, triethylamine, long-chain fat amine or aniline; Said heteropoly acid is molybdophosphate, tungstophosphoric acid, molybdenum silicic acid or tungstosilicic acid.Said long-chain fat amine is that atomicity is C
8-C
22The high-carbon fat primary amine, like behenic amine.Said organic solvent is a methyl alcohol, ethanol, isopropyl alcohol, one or more in the propyl alcohol.
The preparation method of heteropoly acid modified catalyst; Heteropoly acid and amine substance are mixed in the water-soluble or organic solvent under room temperature, stirring condition, then add precipitate in the liquid medium, be the heteropoly acid modified catalyst; Wherein, heteropoly acid and amine substance in molar ratio 1: 0.5-5 mixes.
Said amine substance is a sulfamic acid, ethylenediamine, triethylamine, long-chain fat amine or aniline; Said heteropoly acid is a molybdophosphate, tungstophosphoric acid, molybdenum silicic acid or tungstosilicic acid; Said organic solvent is a methyl alcohol, ethanol, isopropyl alcohol, one or more in the propyl alcohol.
Heteropoly acid modified catalyst catalytic hydrolysis reaction system; The catalytic hydrolysis reaction system is a heterogeneous system; Said heteropoly acid modified catalyst and catalytic reaction substrate same mutually in; Under the stirring condition substrate through the hydrolysis products therefrom be dissolved into automatically solvent mutually in, the heteropoly acid modified catalyst in reaction system automatically the deposition, separate with reaction medium.
Reaction dissolvent is a polar solvent water in the catalytic hydrolysis reaction system, methyl alcohol, ethanol, isopropyl alcohol, one or more in the propyl alcohol.Reaction substrate can be polysaccharose substances such as lipids such as Ethyl formate, ethyl acetate, ethyl propionate or starch, sucrose, cellulose in the catalytic hydrolysis reaction system.
The advantage that the present invention compares with known technology: gained catalyst of the present invention is easy to preparation, and catalytic hydrolysis reaction system safety non-pollution, and catalytic activity is high.Catalyst post catalyst reaction of the present invention is easy to recycle, and product separates with catalyst automatically, is easy to extract, and reaction condition is gentle, is easy to realize industrial applications.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described further.Should be understood that following examples only are used to the present invention is described but not are used to limit scope of the present invention.
Embodiment 1
The 2.88g phosphotungstic acid is dissolved in the 2mL ethanol, and the 0.371g lauryl amine is dissolved in the 10mL ethanol, and two kinds of solution mix, and about magnetic agitation 2h, reaction is carried out fully.In the reactant liquor of complete reaction, add distilled water, separate out this moment and produce a large amount of white precipitates, centrifugal, with the distilled water washing repeatedly, be neutral to cleaning solution.About 100 ℃ of dry 10h, take out, be ground to fine powder and promptly get the heteropoly acid modified catalyst.
Recording this phosphotungstic acid modified catalyst of gained according to nitrogen adsorption desorption test is large pore material, and the aperture is 615.17nm, and unmodified phosphotungstic acid is a pore material, and the aperture has only 9.79nm.
Embodiment 2
The 28.87g silico-tungstic acid is dissolved in the 2mL ethanol, and the 0.371g lauryl amine is dissolved in the 10mL ethanol, and two kinds of solution mix, and about magnetic agitation 2h, reaction is carried out fully.In the reactant liquor of complete reaction, add distilled water, separate out this moment and produce a large amount of white precipitates, centrifugal, with the distilled water washing repeatedly, be neutral to cleaning solution.About 100 ℃ of dry 10h, take out, be ground to fine powder and promptly get the heteropoly acid modified catalyst.
Said heteropoly acid modified catalyst then adds in the liquid medium for heteropoly acid and amine substance are mixed in the water-soluble or organic solvent under stirring condition, and precipitate is the heteropoly acid modified catalyst.
Said amine substance also can be sulfamic acid, ethylenediamine, triethylamine, long-chain fat amine or aniline; Long-chain fat amine is that atomicity is C
8-C
22The high-carbon fat primary amine, like behenic amine.Said heteropoly acid also can be molybdophosphate, tungstophosphoric acid, molybdenum silicic acid or tungstosilicic acid.Said organic solvent is a methyl alcohol, ethanol, isopropyl alcohol, one or more in the propyl alcohol.
Embodiment 3
With 0.3mL ethyl acetate, the heteropolyacid catalyst of 0.3g embodiment 1 mixes and adds test tube, and 15w power is warming up to 70 ℃ of reaction 30min under the microwave condition.Post catalyst reaction and ethyl acetate are deposited to the test tube bottom automatically, after finishing, reaction stops to stir.Get supernatant 1mL, internal standard compound is a butanols, and solution dilutes after 0.22 μ m membrane filtration carries out separation detection on gas-chromatography (GC).Confirm that product is acetate and ethanol,
The ethyl acetate conversion ratio calculates with (certain target product molal quantity)/(molal quantity of ethyl acetate) * 100%, and the correlation computations formula is following:
Ethyl acetate conversion ratio %=n
Ethanol/ n
Ethyl acetate* 100%,
Calculate the ethyl acetate conversion ratio and reach 94.96%.
Embodiment 4
With 0.3mL ethyl acetate, the heteropolyacid catalyst of 0.3g embodiment 1 mixes and adds test tube, and the oil bath reacting by heating time is 5h.Post catalyst reaction and ethyl acetate are deposited to the test tube bottom automatically.Get supernatant 1mL, internal standard compound is a butanols, and solution dilutes after 0.22 μ m membrane filtration carries out separation detection on gas-chromatography (GC).Confirm that product is acetate and ethanol,
The ethyl acetate conversion ratio calculates with (certain target product molal quantity)/(molal quantity of ethyl acetate) * 100%, and the correlation computations formula is following:
Ethyl acetate conversion ratio %=n
Ethanol/ n
Ethyl acetate* 100%,
Calculate the ethyl acetate conversion ratio and reach 63.08%.
Embodiment 5
With 0.3mL ethyl acetate, the heteropolyacid catalyst of 0.3g embodiment 1 mixes and adds test tube, and 15w power is warming up to 70 ℃ of reaction 30mi n under the microwave condition.Post catalyst reaction and ethyl acetate are deposited to the test tube bottom automatically.Catalyst recovery then, and employing reclaims the catalyst hydrolysis of ethyl acetate, and 70 ℃ of temperature during reaction 30min, are got supernatant 1mL, and internal standard compound is a butanols, and solution dilutes after 0.22 μ m membrane filtration carries out separation detection on gas-chromatography (GC).Confirm that product is acetate and ethanol,
The ethyl acetate conversion ratio calculates with (certain target product molal quantity)/(molal quantity of ethyl acetate) * 100%, and the correlation computations formula is following:
Ethyl acetate conversion ratio %=n
Ethanol/ n
Acetate is ester* 100%,
Calculate the ethyl acetate conversion ratio and reach 89.21%.
Embodiment 6
With 0.02g sucrose, the heteropolyacid catalyst of 0.02g embodiment 1 mixes and adds test tube, and 15w power is warming up to 70 ℃ of reaction 2h under the microwave condition.Post catalyst reaction and sucrose are deposited to the test tube bottom automatically.Reaction finishes rear catalyst and is deposited to the test tube bottom.Adopt the glucose ELIASA to measure the product concentration of glucose.
Sucrose hydrolysis rate %=n
Glucose/ n
Sucrose* 100%.
Calculate the sucrose hydrolysis rate and reach 88%.
Embodiment
With 0.02g sucrose, the heteropolyacid catalyst of 0.02g embodiment 1 mixes and adds test tube, and 15w power is warming up to 75 ℃ of reaction 2h under the microwave condition.Post catalyst reaction and sucrose are deposited to the test tube bottom automatically.Reaction finishes rear catalyst and is deposited to the test tube bottom.Adopt the glucose ELIASA to measure the product concentration of glucose.
Sucrose hydrolysis rate %=n
Glucose/ n
Sucrose* 100%.
Calculate the sucrose hydrolysis rate and reach 100%.
Embodiment 7
With 0.02g sucrose, the heteropolyacid catalyst of 0.02g embodiment 1 mixes and adds test tube, and 15w power is warming up to 75 ℃ of reaction 2h under the microwave condition.Post catalyst reaction and sucrose are deposited to the test tube bottom automatically.Reaction finishes rear catalyst and is deposited to the test tube bottom.Catalyst recovery then, and employing reclaims the hydrolysis of catalyst sucrose hydrolysis, and 75 ℃ of temperature during reaction 2h, adopt the glucose ELIASA to measure the product concentration of glucose.
Sucrose hydrolysis rate %=n
Glucose/ n
Sucrose* 100%.
Calculate the sucrose hydrolysis rate and reach 100%.
The above specific embodiment is only unrestricted in order to technical scheme of the present invention to be described; Although the present invention is specified with reference to instance; Those of ordinary skill in the art is to be understood that; Can make amendment or be equal to replacement technical scheme of the present invention, and not break away from the spirit and the scope of technical scheme of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (9)
1. heteropoly acid modified catalyst is characterized in that: the heteropoly acid modified catalyst is in molar ratio 1: heteropoly acid and amine substance that 0.5-5 mixes.
2. by the described heteropoly acid modified catalyst of claim 1; It is characterized in that: said heteropoly acid modified catalyst is for mixing heteropoly acid and amine substance under stirring condition in the water-soluble or organic solvent; Then add in the liquid medium, precipitate is the heteropoly acid modified catalyst.
3. by claim 1 or 2 described heteropoly acid modified catalysts, it is characterized in that: said amine substance is a sulfamic acid, ethylenediamine, triethylamine, long-chain fat amine or aniline; Said heteropoly acid is molybdophosphate, tungstophosphoric acid, molybdenum silicic acid or tungstosilicic acid.
4. by the described heteropoly acid modified catalyst of claim 3, it is characterized in that: said long-chain fat amine is that atomicity is C
8-C
22The high-carbon fat primary amine.
5. by the described heteropoly acid modified catalyst of claim 2, it is characterized in that: said organic solvent is a methyl alcohol, ethanol, isopropyl alcohol, one or more in the propyl alcohol.
6. the preparation method of the described heteropoly acid modified catalyst of claim 1; It is characterized in that: heteropoly acid and amine substance are mixed in the water-soluble or organic solvent under room temperature, stirring condition; Then add precipitate in the liquid medium; Be the heteropoly acid modified catalyst, wherein, heteropoly acid and amine substance in molar ratio 1: 0.5-5 mixes.
7. by the preparation method of the described heteropoly acid modified catalyst of claim 6, it is characterized in that: said amine substance is a sulfamic acid, ethylenediamine, triethylamine, long-chain fat amine or aniline; Said heteropoly acid is a molybdophosphate, tungstophosphoric acid, molybdenum silicic acid or tungstosilicic acid; Said organic solvent is a methyl alcohol, ethanol, isopropyl alcohol, one or more in the propyl alcohol.
8. the described heteropoly acid modified catalyst of claim 1 catalytic hydrolysis reaction system; It is characterized in that: the catalytic hydrolysis reaction system is a heterogeneous system; Said heteropoly acid modified catalyst and catalytic reaction substrate same mutually in; Under the stirring condition substrate through the hydrolysis products therefrom be dissolved into automatically solvent mutually in, the heteropoly acid modified catalyst in reaction system automatically the deposition, separate with reaction medium.
9. the described heteropoly acid modified catalyst of claim 8 catalytic hydrolysis reaction system, it is characterized in that: reaction dissolvent is a polar solvent water in the catalytic hydrolysis reaction system, methyl alcohol, ethanol, isopropyl alcohol, one or more in the propyl alcohol.
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Cited By (5)
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|---|---|---|---|---|
| CN104368386A (en) * | 2014-11-12 | 2015-02-25 | 聊城大学 | Heteropoly acid modified catalyst as well as preparation method and application thereof |
| CN105504350A (en) * | 2015-12-23 | 2016-04-20 | 中国科学院宁波材料技术与工程研究所 | Polyoxometalate based flame retardant synergists and application thereof |
| CN106008206A (en) * | 2016-05-31 | 2016-10-12 | 邵阳学院 | Method for dodecylamine phosphotungstate catalyzed synthesis of long-chain carboxylate |
| CN109225323A (en) * | 2018-10-26 | 2019-01-18 | 闽江学院 | Sulfonic group is functionalized organic/inorganic dication-vanadium doping heteropolyacid anions composite hybridization body and its synthesis and application |
| CN112169841A (en) * | 2020-10-23 | 2021-01-05 | 长春工业大学 | Preparation method of palladium or platinum and heteropoly acid co-loaded nanoporous carbon composite material |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104368386A (en) * | 2014-11-12 | 2015-02-25 | 聊城大学 | Heteropoly acid modified catalyst as well as preparation method and application thereof |
| CN104368386B (en) * | 2014-11-12 | 2016-05-11 | 聊城大学 | A kind of heteropoly acid modified catalyst and preparation and application thereof |
| CN105504350A (en) * | 2015-12-23 | 2016-04-20 | 中国科学院宁波材料技术与工程研究所 | Polyoxometalate based flame retardant synergists and application thereof |
| CN106008206A (en) * | 2016-05-31 | 2016-10-12 | 邵阳学院 | Method for dodecylamine phosphotungstate catalyzed synthesis of long-chain carboxylate |
| CN106008206B (en) * | 2016-05-31 | 2018-10-23 | 邵阳学院 | A kind of method that phosphotungstic acid lauryl amine salt catalyzes and synthesizes higher fatty ester |
| CN109225323A (en) * | 2018-10-26 | 2019-01-18 | 闽江学院 | Sulfonic group is functionalized organic/inorganic dication-vanadium doping heteropolyacid anions composite hybridization body and its synthesis and application |
| CN109225323B (en) * | 2018-10-26 | 2021-07-27 | 闽江学院 | Sulfonic group functionalized organic/inorganic dication-vanadium doped heteropoly acid anion composite hybrid and synthesis and application thereof |
| CN112169841A (en) * | 2020-10-23 | 2021-01-05 | 长春工业大学 | Preparation method of palladium or platinum and heteropoly acid co-loaded nanoporous carbon composite material |
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Application publication date: 20120822 |