CN102553647A - Magnetic nanometer solid acid catalyst and preparation method thereof - Google Patents

Magnetic nanometer solid acid catalyst and preparation method thereof Download PDF

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Publication number
CN102553647A
CN102553647A CN2012100043489A CN201210004348A CN102553647A CN 102553647 A CN102553647 A CN 102553647A CN 2012100043489 A CN2012100043489 A CN 2012100043489A CN 201210004348 A CN201210004348 A CN 201210004348A CN 102553647 A CN102553647 A CN 102553647A
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acid
catalyst
magnetic nano
particle
chitosan
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单永奎
韩振
孔爱国
周维
孔莹莹
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East China Normal University
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East China Normal University
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Abstract

The invention discloses a magnetic nanometer solid acid catalyst and a preparation method of the magnetic nanometer solid acid catalyst. The catalyst is formed by taking magnetic nanometer particles as a core and adopting heteropolyacid functionalized crosslinked chitosan to wrap and decorate the magnetic nanometer particles, and the magnetic nanometer particles as a core is the oxide, metal and alloy of superparamagnetic iron; the crosslinked chitosan is a high polymer formed by taking chitosan as a presoma and adopting dialdehyde compounds as cross-linking agent to crosslink; and the heteropolyacid is in the type of a keggin structure and contains essential water or crystallization water with inconstant quantity in a crystal state or an amorphous state. The preparation method is achieved by the steps of taking the magnetic nanometer particles, the chitosan, the cross-linking agent and the heteropolyacid as raw materials, adding the raw materials to a reactor in sequence, and reacting sequentially in the reactor. The catalyst is free from separation of any intermediate products during preparation, has high catalytic activity, is easy for separation and recovery, can be utilized repeatedly, and is beneficial to application in industrialized catalysis.

Description

A kind of magnetic nano solid acid catalyst and preparation method thereof
Technical field
The present invention relates to catalytic chemistry and nano material preparation technical field, specifically a kind of magnetic nano solid acid catalyst of heteropoly acid functionalization and preparation method.
Background technology
For liquid acid, solid acid have hypotoxicity, not corrosive equipment, environmental friendliness, be prone to reclaim advantage such as can be recycled and getting most of the attention.For many years, people are seeking the solid acid industrial catalyst that exploitation can replace liquid acid always.Heteropoly acid is to it is found that one of solid acid catalyst material the earliest, because its highly acid, and low-corrosiveness and high catalytic activity and obtain extensive concern.And in many large-scale Industrial Catalysis, be applied.Yet, its lower surface area with the solution of polarity in higher solubility, and the difficulty on aspect the recovery; Limited the extensive use of heteropoly acid in industry, in order to overcome these shortcomings, people have done a lot of effort; Such as with the pillared layered clay of heteropoly acid; Heteropoly acid is immobilized on the molecular sieve of high surface area, or with the heteropoly acid grafting on organic polymer, or prepare nano level heteropolyacid salt particle etc.But, from the practical application angle, still exist heteropoly acid and be prone to run off, active low, poor stability, the difficult defective that reclaims.
In the last few years, nano science and nanometer technology develop rapidly had brought rare opportunity for the development of solid acid industrial catalyst.People have made a large amount of effort for the research of magnetic nano-catalyst capable of circulation, and seminar of Beijing University of Chemical Technology successfully prepares magnetic nano solid acid catalyst ZrO 2/ Fe 3O 4, ZrO 2/ Fe 3O 4This catalyst series of experiment confirm all has and is easy to reclaim through magnetic field, the advantage that service life is long.Shao Yanqiu etc. utilize sol-gel method, the precipitation method to prepare solid super acid catalyst TiO 2/ Fe 3O 4With its activity of esterification test of acetate and n-butanol, point out to have more excellent magnetism and catalytic activity than catalyst with precipitation method preparation with sol-gel method; The concentration of the mol ratio of Ti and Fe, sintering temperature and maceration extract is the principal element that influences catalytic performance and magnetic.Recently; C.W. Jones etc. has reported that several kinds of dissimilar sulfonate functional coated with silica magnetic nano-particle solid acid catalysts have good catalytic activity in benzaldehyde dimethylacetal hydrolysis; And problems such as the difficult separation of catalyst have been solved; But synthetic such catalyst equally also exists reagent to cost an arm and a leg, and problems such as building-up process complicacy restrict its extensive use in industry.
Magnetic solid acid catalyst has been studied for many years some catalytic reaction; But the various magnetic solid acid catalysts of at present having developed; Also there is more deficiency, problem such as it is wide that, intensity difference less relatively, on the high side like the acid amount of unit mass, low temperature active are poor, acid strength distributes, therefore; To the architectural feature and the performance of the different characteristics of each reaction design catalyst, might develop the high magnetic solid acid catalyst of a new generation.Summary of the invention
The purpose of this invention is to provide a kind of novel magnetic nano solid acid catalyst and preparation method thereof, adopt the method preparation of " treating different things alike ", the gained catalyst is active high, and easily separated recovery can reuse, and is beneficial to Industrial Catalysis and uses.
The objective of the invention is to realize like this:
A kind of magnetic nano solid acid catalyst, characteristics are to be nuclear with the magnetic nano-particle, with the magnetic retention acid catalytic material that forms behind the heteropoly acid functionalization cross-linked chitosan coating decoration magnetic nano-particle.
Nano particle as magnetic core in the magnetic nano solid acid catalysis material provided by the invention is oxide, metal and the alloy of superparamagnetism iron, like Fe 3O 4, Ni, Co, FePt and FePd etc.
Cross-linked chitosan of the present invention is to be presoma with the shitosan, containing the compound of dialdehyde-based, as glyoxal, MDA, butanedial, glutaraldehyde, hexandial, heptan dialdehyde or suberic aldehyde etc. be the crosslinked high molecular polymer that forms of crosslinking agent.
Heteropoly acid of the present invention is to belong to keggin structure type heteropoly acid, like silico-tungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid etc., contains number indefinite the composition water or the crystallization water in crystalline state and amorphous state.
Heteropoly acid functionalization cross-linked chitosan of the present invention is to belong to heteropoly acid to combine salify with amino in the cross-linked chitosan; From but heteropoly acid be fixed on the cross-linked chitosan of coated magnetic nano particle, and make the cross-linked chitosan of coated magnetic nano particle have acid and certain acid amount.
Said magnetic nano solid acid catalyst preparation method is to be raw material with magnetic nano-particle, shitosan, crosslinking agent and heteropoly acid, adds a reactor according to sequencing, and the preparation of material is in a reactor, to accomplish through reaction successively.In the process of preparation, has no intermediate product separated (method of promptly " treating different things alike ").
A kind of preparation method of magnetic nano solid acid catalyst, concrete detailed preparation process may further comprise the steps:
The first step: shitosan is joined in acid (the hydrochloric acid molar fraction is 0.05mol/L to 0.1mol/L for sulfuric acid, the acetate) solution, be stirred to whole dissolvings;
Second step: the magnetic nano-particle (nano particle is 0.1-15 with the ratio of chitosan mass) of prepared fresh is distributed to the above-mentioned chitosan solution that makes, and mechanical agitation is heated to 20-90 ℃ simultaneously;
The 3rd step: drip cross-linking agent solution (crosslinking agent is 0.1-10 with the ratio of chitosan mass) to above-mentioned mixture system, continue heating 1-10h down, make to react completely, and make tightly coated magnetic nano particle of cross-linked chitosan at 40-95 ℃.
The 4th step: under heating and well-beaten condition; Be dissolved with heteropoly acid solution (heteropoly acid is 0.1-100 with the ratio of chitosan mass) to above-mentioned mixture system adding, when treating not generate the sediment generation, stop to stir; Static; Magnetic Isolation goes out sediment, spends deionised water, and dry back products therefrom is the magnetic nano-particle solid acid catalyst of heteropoly acid functionalization cross-linked chitosan coating decoration.
Beneficial effect of the present invention:
1, abundant raw material is easy to get, low price, and toxicity is little.The magnetic nano-particle solid acid catalyst material of prepared heteropoly acid functionalization cross-linked chitosan coating decoration has biodegradable.
2, synthesis step is simple, and is easy to operate, and productive rate is high, and repeating effect is good, is beneficial to large-scale industrial production.
3, catalyst of the present invention is active high, and easily separated recovery can reuse, and is beneficial to Industrial Catalysis and uses.
The specific embodiment
Through following specific embodiment the present invention is done further detailed description.
Embodiment 1
The 0.5g shitosan is joined in the 0.05mol/L acetic acid solution, stir 8h under the room temperature shitosan is dissolved fully, the magnetic Fe of 0.5g prepared fresh 3O 4Nano particle is distributed to the aforementioned chitosan solution that makes, and ultrasonic Treatment 30min is under mechanical agitation; After being heated to 20 ℃, begin to drip 10ml glutaraldehyde solution (mass fraction is 15%), after 30min drips off; Continuation is heated 1h down at 20 ℃; And then be warming up to 60 ℃ of insulation 1h, reaction is carried out fully, and made cross-linked chitosan tightly coat Fe 3O 4Nano particle; Add 100ml subsequently fast and be dissolved with 3g silico-tungstic acid (H 4SiW 12O 40XH 2O) the aqueous solution generates a large amount of grey black sediments, behind the 30min, stops to stir.Static back Magnetic Isolation goes out bottom grey black sediment, uses deionized water, and ethanol repeatedly washs, and removes absorption above that not by immobilized heteropoly acid molecule.Clean back dry 8h under 60 ℃ of vacuum conditions, products therefrom is the magnetic nano-particle solid acid catalyst of heteropoly acid functionalization cross-linked chitosan coating decoration.
Embodiment 2
The 5g shitosan is joined in the 0.1mol/L acetic acid solution, stir 8h under the room temperature shitosan is dissolved fully, the Ni nano particle of 0.5g prepared fresh is distributed to the aforementioned chitosan solution that makes; Ultrasonic Treatment 30min, under mechanical agitation, be heated to 40 ℃ after; Beginning Dropwise 35 ml glutaraldehyde solution (mass fraction is 15%); After 30min drips off, continue to heat 1h down, and then be warming up to 80 ℃ of insulation 1h at 40 ℃; Reaction is carried out fully, and made cross-linked chitosan tightly coat the Ni nano particle; Add 100ml subsequently fast and be dissolved with 0.5g silico-tungstic acid (H 4SiW 12O 40XH 2O) the aqueous solution generates a large amount of grey black sediments, behind the 30min, stops to stir.Static back Magnetic Isolation goes out bottom grey black sediment, uses deionized water, and ethanol repeatedly washs, and removes absorption above that not by immobilized heteropoly acid molecule.Clean back dry 8h under 60 ℃ of vacuum conditions, products therefrom is the magnetic nano-particle solid acid catalyst of heteropoly acid functionalization cross-linked chitosan coating decoration.
Embodiment 3
The 0.5g shitosan is joined in the 0.05mol/L hydrochloric acid solution, stir 8h under the room temperature shitosan is dissolved fully, the Co nano particle of 7.5g prepared fresh is distributed to the aforementioned chitosan solution that makes; Ultrasonic Treatment 30min, under mechanical agitation, be heated to 40 ℃ after; Begin to drip 10ml glutaraldehyde solution (mass fraction is 15%); After 30min drips off, continue to heat 1h down, and then be warming up to 95 ℃ of insulation 1h at 40 ℃; Reaction is carried out fully, and made cross-linked chitosan tightly coat the Co nano particle; Add 100ml subsequently fast and be dissolved with 0.5g silico-tungstic acid (H 4SiW 12O 40XH 2O) the aqueous solution generates a large amount of grey black sediments, behind the 30min, stops to stir.Static back Magnetic Isolation goes out bottom grey black sediment, uses deionized water, and ethanol repeatedly washs, and removes absorption above that not by immobilized heteropoly acid molecule.Clean back dry 8h under 60 ℃ of vacuum conditions, products therefrom is the magnetic nano-particle solid acid catalyst of heteropoly acid functionalization cross-linked chitosan coating decoration.
Embodiment 4
The 1.0g shitosan is joined in the 0.05mol/L sulfuric acid solution, stir 8h under the room temperature shitosan is dissolved fully, the FePt nano particle of 1.0g prepared fresh is distributed to the aforementioned chitosan solution that makes; Ultrasonic Treatment 30min, under mechanical agitation, be heated to 90 ℃ after; Begin to drip 20ml suberic aldehyde solution (mass fraction is 15%); After 30min drips off, continue to heat 1h down, and then be warming up to 95 ℃ of insulation 1h at 90 ℃; Reaction is carried out fully, and made cross-linked chitosan tightly coat the FePt nano particle; Add 100ml subsequently fast and be dissolved with 2.5g silico-tungstic acid (H 4SiW 12O 40XH 2O) the aqueous solution generates a large amount of grey black sediments, behind the 30min, stops to stir.Static back Magnetic Isolation goes out bottom grey black sediment, uses deionized water, and ethanol repeatedly washs, and removes absorption above that not by immobilized heteropoly acid molecule.Clean back dry 8h under 60 ℃ of vacuum conditions, products therefrom is the magnetic nano-particle solid acid catalyst of heteropoly acid functionalization cross-linked chitosan coating decoration.
Embodiment 5
The 1.0g shitosan is joined in the 0.1mol/L hydrochloric acid solution, stir 8h under the room temperature shitosan is dissolved fully, the FePd nano particle of 1.0g prepared fresh is distributed to the aforementioned chitosan solution that makes; Ultrasonic Treatment 30min, under mechanical agitation, be heated to 40 ℃ after; Begin to drip 20ml hexandial solution (mass fraction is 15%); After 30min drips off, continue to heat 1h down, and then be warming up to 80 ℃ of insulation 1h at 60 ℃; Reaction is carried out fully, and made cross-linked chitosan tightly coat the FePd nano particle; Add 100ml subsequently fast and be dissolved with 2.5g silico-tungstic acid (H 4SiW 12O 40XH2O) the aqueous solution generates a large amount of grey black sediments, behind the 30min, stops to stir.Static back Magnetic Isolation goes out bottom grey black sediment, uses deionized water, and ethanol repeatedly washs, and removes absorption above that not by immobilized heteropoly acid molecule; Clean back dry 8h under 60 ℃ of vacuum conditions, products therefrom is the magnetic nano-particle solid acid catalyst of heteropoly acid functionalization cross-linked chitosan coating decoration.
Embodiment 6
Substitute the hexandial solution in " embodiment 5 " with 20ml glyoxal solution (mass fraction is 15%); Repeat the preparation process that " embodiment 5 " are described, can obtain with the glyoxal is the magnetic nano-particle solid acid catalyst of heteropoly acid functionalization cross-linked chitosan coating decoration of crosslinking agent preparation.
Embodiment 7
Substitute the hexandial solution in " embodiment 5 " with 20ml MDA solution (mass fraction is 15%); Repeat the preparation process that " embodiment 5 " are described, can obtain with the MDA is the magnetic nano-particle solid acid catalyst of heteropoly acid functionalization cross-linked chitosan coating decoration of crosslinking agent preparation.
Embodiment 8
Substitute the hexandial solution in " embodiment 5 " with 20ml butanedial solution (mass fraction is 15%); Repeat the preparation process that " embodiment 5 " are described, can obtain with the butanedial is the magnetic nano-particle solid acid catalyst of heteropoly acid functionalization cross-linked chitosan coating decoration of crosslinking agent preparation.
Embodiment 9
Substitute the hexandial solution in " embodiment 5 " with 20ml dialdehyde in heptan solution (mass fraction is 15%); Repeat the preparation process that " embodiment 5 " are described, can obtain with heptan dialdehyde be the magnetic nano-particle solid acid catalyst of the heteropoly acid functionalization cross-linked chitosan coating decoration of crosslinking agent preparation.
Embodiment 10
The 1.0g shitosan is joined in the 0.1mol/L sulfuric acid solution, stir 8h under the room temperature shitosan is dissolved fully, the Fe of 1.0g prepared fresh 3O 4Nano particle is distributed to the above-mentioned chitosan solution that makes, and ultrasonic Treatment 30min is under mechanical agitation; After being heated to 40 ℃, begin to drip 20ml glutaraldehyde solution (mass fraction is 15%), after 30min drips off; Continue heating 1h down at 60 ℃; And then be warming up to 80 ℃ of insulation 1h, reaction is carried out fully, and made cross-linked chitosan tightly coat Fe 3O 4Nano particle; Add 100ml subsequently fast and be dissolved with 5g silicomolybdic acid (H 4SiMo 12O 40XH 2O) the aqueous solution generates a large amount of taupe brown sediments, behind the 30min, stops to stir.Static back Magnetic Isolation goes out bottom taupe brown sediment, uses deionized water, and ethanol repeatedly washs, and removes absorption above that not by immobilized heteropoly acid molecule.Clean back dry 8h under 60 ℃ of vacuum conditions, products therefrom is the magnetic nano-particle solid acid catalyst of heteropoly acid functionalization cross-linked chitosan coating decoration.
Embodiment 11
Be dissolved with 5g phosphomolybdic acid (H with 100ml 4PMo 12O 40XH 2O) the aqueous solution; Substitute the silicomolybdic acid aqueous solution in " embodiment 10 "; Repeat the preparation process that " embodiment 10 " are described, can obtain with the phosphomolybdic acid is the magnetic nano-particle solid acid catalyst of heteropoly acid functionalization cross-linked chitosan coating decoration of functionalized reagent preparation.
Embodiment 12
Be dissolved with 5g phosphotungstic acid (H with 100ml 4PW 12O 40XH 2O) the aqueous solution; Substitute the silicomolybdic acid aqueous solution in " embodiment 10 "; Repeat the preparation process that " embodiment 10 " are described, can obtain with the phosphotungstic acid is the magnetic nano-particle solid acid catalyst of heteropoly acid functionalization cross-linked chitosan coating decoration of functionalized reagent preparation.
Embodiment 13
The 0.5g shitosan is joined in the 0.05mol/L acetic acid solution, stir 8h under the room temperature shitosan is dissolved fully, the FePt nano particle of 1.0g prepared fresh is distributed to the aforementioned chitosan solution that makes; Ultrasonic Treatment 30min, under mechanical agitation, be heated to 40 ℃ after; Begin to drip 10ml glutaraldehyde solution (mass fraction is 15%); After 30min drips off, continue to heat 1h down, and then be warming up to 80 ℃ of insulation 1h at 60 ℃; Reaction is carried out fully, and made cross-linked chitosan tightly coat the FePt nano particle; Add 150ml subsequently fast and be dissolved with 50g silico-tungstic acid (H 4SiW 12O 40XH 2O) the aqueous solution generates a large amount of grey black sediments, behind the 30min, stops to stir.Static back Magnetic Isolation goes out bottom grey black sediment, uses deionized water, and ethanol repeatedly washs, and removes absorption above that not by immobilized heteropoly acid molecule.Clean back dry 8h under 60 ℃ of vacuum conditions, products therefrom is the magnetic nano-particle solid acid catalyst of heteropoly acid functionalization cross-linked chitosan coating decoration.
Embodiment 14
The 1.5g shitosan is joined in the 0.05mol/L acetic acid solution, stir 8h under the room temperature shitosan is dissolved fully, again the Fe of 2.5g prepared fresh 3O 4Nano particle is distributed to the above-mentioned chitosan solution that makes, ultrasonic 30min, under mechanical agitation, be heated to 40 ℃ simultaneously after; Beginning Dropwise 35 ml glutaraldehyde solution (mass fraction is 15%); After 30min drips off, continue to be heated to 60 ℃ of insulation 1h, be warming up to 80 ℃ of heating 1h again; Make reaction carry out making cross-linked chitosan tightly coat Fe fully 3O 4Nano particle; Then add 100ml fast and be dissolved with 5g silico-tungstic acid (H 4SiW 12O 40XH 2O) solution generates a large amount of grey black sediments, behind the 30min; Stop reaction, Magnetic Isolation goes out bottom grey black sediment, uses deionized water; Ethanol repeatedly washs; Remove absorption above that not by immobilized heteropoly acid molecule, clean the back at 60 ℃ of vacuum drying 8h, products therefrom is the magnetic nano-particle solid acid catalyst of heteropoly acid functionalization cross-linked chitosan coating decoration.
Practical example 1
The magnetic nano-particle solid acid catalyst material of heteropoly acid functionalization cross-linked chitosan coating decoration with " embodiment 14 " preparation is a catalyst; With benzaldehyde and ethylene glycol is raw material; Having electromagnetic agitation; Reflux condensing tube in the 100 mL three-necked bottles of water knockout drum, carries out catalysis synthesizing benzaldehyde Glycol Acetal.Its reaction condition is: (catalyst/PhCHO)=0.6%, band aqua cyclohexane are 47.5mmol to the mass ratio of the mol ratio=10:1 of ethylene glycol and benzaldehyde (EG=6.20g, PhCHO=1.06g), catalyst and benzaldehyde, and reaction temperature is that 354K, reaction time are 2h.Water and cyclohexane azeotropic that reflux in the course of reaction, strong agitation produce reaction steam.After reaction stopped, adding excess ethanol solution carried out the Magnetic Isolation catalyst with permanent magnet, toppled over upper solution, as interior mark, adopted internal standard method to carry out the GC test with toluene, calculated product yield and reached 99%, and selectivity is 100%,
Practical example 2
After isolated catalyst repeatedly washs with ethanol in " practical example 1 "; 80 ℃ of dry 8h of vacuum drying chamber; And as catalyst; With device described in " practical example 2 ", under the reaction condition described in " practical example 1 ", carry out catalysis synthesizing benzaldehyde Glycol Acetal again, be used to realize the recycle of catalyst; Utilize the analytical described in " practical example 1 " to obtain; This catalyst is through behind 6 circulation experiments; Do not find that its catalytic activity has the phenomenon of obvious reduction; Product benzaldehyde Glycol Acetal yield all can remain on about 99%, has realized the separation of catalyst rapid magnetic and has repeatedly recycled.

Claims (6)

1. magnetic nano solid acid catalyst; It is characterized in that this catalyst is is nuclear with the magnetic nano-particle; With behind the heteropoly acid functionalization cross-linked chitosan coating decoration magnetic nano-particle and form, the magnetic nano-particle of its nuclear is oxide, metal and the alloy of superparamagnetism iron; Heteropoly acid is a keggin structure type heteropoly acid, contains number indefinite the composition water or the crystallization water in crystalline state and amorphous state; Cross-linked chitosan is to be presoma with the shitosan, is the crosslinked high molecular polymer that forms of crosslinking agent with the compound that contains dialdehyde-based.
2. catalyst according to claim 1 is characterized in that oxide, metal and the alloy of said superparamagnetism iron is Fe 3O 4, Ni, Co, FePt and FePd.
3. catalyst according to claim 1 is characterized in that said keggin structure type heteropoly acid is silico-tungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid.
4. catalyst according to claim 1, it is characterized in that the said compound that contains dialdehyde-based be glyoxal, MDA, butanedial, glutaraldehyde, hexandial, heptan dialdehyde or suberic aldehyde.
5. the preparation method of the said magnetic nano solid acid catalyst of claim 1 is characterized in that shitosan is joined in the acid solution, magnetic nano-particle is under agitation heated again, and evenly spreads in the aforesaid shitosan acid solution; Drip cross-linking agent solution, and then heat up, reaction 1-10h; Under heating and well-beaten condition, add heteropoly acid solution, when having treated that sediment generates; Stop to stir, static, Magnetic Isolation goes out sediment; Spend deionised water, drying, products therefrom is said magnetic nano solid acid catalyst; Wherein: nano particle is 0.1-15 with the ratio of chitosan mass; Heteropoly acid is 0.1-100 with the ratio of chitosan mass; Crosslinking agent is 0.1-10 with the ratio of chitosan mass; Said acid solution is sulfuric acid, acetate or hydrochloric acid solution, and molar fraction is 0.05mol/L to 0.1mol/L; Said heating-up temperature is 20-90 ℃, and the intensification temperature is 40-95 ℃.
6. method according to claim 5 is characterized in that said acid solution is sulfuric acid, acetate or hydrochloric acid solution, and molar fraction is 0.05mol/L to 0.1mol/L.
CN2012100043489A 2012-01-09 2012-01-09 Magnetic nanometer solid acid catalyst and preparation method thereof Pending CN102553647A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104437655A (en) * 2014-11-18 2015-03-25 成都理想财富投资咨询有限公司 Preparation method of magnetic solid acid catalyst for konjac flying powder
CN107159136A (en) * 2017-04-25 2017-09-15 蒋丽红 A kind of preparation method of blood toxicity adsorbent
CN107890882A (en) * 2017-11-07 2018-04-10 济南大学 A kind of method that dipping polymerization method prepares peracid density solid catalyst
CN108355700A (en) * 2018-03-02 2018-08-03 河北科技大学 Polyoxometallate and its compound, preparation method and application
CN110586186A (en) * 2019-08-13 2019-12-20 中北大学 High-dispersion polyoxometallate magnetic microsphere catalyst and preparation method and application thereof
CN111326302A (en) * 2020-03-23 2020-06-23 成都新柯力化工科技有限公司 Core-shell structure magnetic material for industrial clean air and preparation method thereof
CN116273159A (en) * 2022-12-05 2023-06-23 中国人民解放军军事科学院系统工程研究院 Sulfonated immobilized binary catalyst, preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101733148A (en) * 2008-11-21 2010-06-16 中国科学院化学研究所 Magnetic heteropolyacid catalyst, preparing method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101733148A (en) * 2008-11-21 2010-06-16 中国科学院化学研究所 Magnetic heteropolyacid catalyst, preparing method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
AIGUO KONG，ET.AL: "One-pot fabrication of magnetically recoverable acid nanocatalyst，heteropolyacids/chitosan/Fe3O4, and its catalytic performance", 《APPLIED CATALYSIS A: GENERAL》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104437655A (en) * 2014-11-18 2015-03-25 成都理想财富投资咨询有限公司 Preparation method of magnetic solid acid catalyst for konjac flying powder
CN107159136A (en) * 2017-04-25 2017-09-15 蒋丽红 A kind of preparation method of blood toxicity adsorbent
CN107890882A (en) * 2017-11-07 2018-04-10 济南大学 A kind of method that dipping polymerization method prepares peracid density solid catalyst
CN108355700A (en) * 2018-03-02 2018-08-03 河北科技大学 Polyoxometallate and its compound, preparation method and application
CN108355700B (en) * 2018-03-02 2020-12-01 河北科技大学 Polyoxometallate and compound, preparation method and application thereof
CN110586186A (en) * 2019-08-13 2019-12-20 中北大学 High-dispersion polyoxometallate magnetic microsphere catalyst and preparation method and application thereof
CN111326302A (en) * 2020-03-23 2020-06-23 成都新柯力化工科技有限公司 Core-shell structure magnetic material for industrial clean air and preparation method thereof
CN116273159A (en) * 2022-12-05 2023-06-23 中国人民解放军军事科学院系统工程研究院 Sulfonated immobilized binary catalyst, preparation method and application thereof
CN116273159B (en) * 2022-12-05 2023-11-17 中国人民解放军军事科学院系统工程研究院 Sulfonated immobilized binary catalyst, preparation method and application thereof

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Application publication date: 20120711