CN104353476A - Preparation method of solid-supported phosphotungstic heteropoly acid - Google Patents
Preparation method of solid-supported phosphotungstic heteropoly acid Download PDFInfo
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- CN104353476A CN104353476A CN201410570479.2A CN201410570479A CN104353476A CN 104353476 A CN104353476 A CN 104353476A CN 201410570479 A CN201410570479 A CN 201410570479A CN 104353476 A CN104353476 A CN 104353476A
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Abstract
The invention discloses a method for preparing solid-supported phosphotungstic heteropoly acid by a diethyl ether/polyaniline extraction process in order to simplify a preparation process of solid-supported heteropoly acid, and solves the problems of resource waste, air environment pollution and the like caused by use of a large amount of diethyl ether for extraction in a conventional preparation process of heteropoly acid. The method comprises the following steps: 1, preparing a diethyl ether/polyaniline extraction agent; 2, preparing solid-supported phosphotungstic heteropoly acid. Through the method, phosphotungstic heteropoly acid in reaction liquid can be extracted by the diethyl ether/polyaniline extraction agent, so that the preparation process of solid-supported phosphotungstic heteropoly acid can be simplified and the problems of resource waste, difficult recycling and the like caused by use of a large amount of diethyl ether for extraction in the conventional preparation process of phosphotungstic heteropoly acid are solved; meanwhile, the method has environmental protection significance.
Description
Technical field
What the present invention proposed is the method preparing solid-carrying type phosphorus heteropoly tungstic acid with ether/polyaniline extractant extraction.
Background technology
Along with the fast development of petrochemical industry and fine chemistry industry, the multifunctionality of catalysis material becomes the fresh target of research; Develop environmentally friendly catalyst to use in Chemical Manufacture and come into one's own.Heteropoly acid is the bi-functional catalyst that a kind of Acidity of Aikalinity and oxidation-reduction quality have concurrently, and the research for new catalytic process is significant.
Heteropoly acid Stability Analysis of Structures, has six unique side's cage structures, can be used in homogeneous phase or heterogeneous catalysis environment, also jointly can use with phase transfer catalyst; The reactivity of heteropoly acid catalysis is high, selective good, is widely used in analytical chemistry, surface chemistry, pharmaceutical chemistry, electrochemistry, Food Chemistry, photochemistry, multiple field such as catalytic chemistry and chemical industry.Heteropoly acid, as the eco-friendly catalyst of one, can reduce the pollution of corrosion to equipment and environment; But preparing in phosphorus heteropoly tungstic acid process in routine, use a large amount of ether to extract phosphorus heteropoly tungstic acid reactant liquor, obtain light yellow clear grease ether-phosphorus heteropoly tungstic acid, then purge ether with air, obtain the light yellow phosphorus heteropoly tungstic acid solid of product; And the ether used in whole extraction process is difficult to be recycled, and causes the problem such as the wasting of resources and environmental pollution.
Heteropoly acid has the long-pending (S.A.<10m of very small specific surface simultaneously
2/ g), belong to non-hole solid matter, its Surface acidity is little, and reactivity is little, and the shortcoming such as not easily separated in homogeneous reaction, limit its scope of application.And supported heteropolyacid not only has all characteristics of conventional heteropoly acid, also have after reacting with the advantages such as the easily separated recovery of product, receive the concern of people; On suitable carrier, make catalyst by immobilized for heteropoly acid simultaneously, not only considerably increase the specific area of catalyst, achieve heterogeneous catalysis, also enhance mechanical strength and the heat endurance of catalyst, overcome the corrosivity of acid to equipment, therefore solid-carrying heteropolyacid catalyst studies more a kind of Multifunction catalyst in Industrial Catalysis.Current domestic and international many scientific research personnel are at research supported heteropolyacid, but the preparation method of common supported heteropolyacid is after first synthesizing and preparing heteropoly acid solid, heteropoly acid solid will be synthesized again and be mixed with the heteropoly acid aqueous solution, then remove the heteropoly acid in adsorption aqueous solution with suitable carrier; Conventional preparation method is infusion process and absorption method, and it is relatively all undesirable that these two kinds of methods obtain load factor.Therefore develop one to prepare supported heteropolyacid new method there is economy and environmental protection double meaning.
Summary of the invention
In order to shorten the preparation technology of supported heteropolyacid, the present invention proposes to utilize ether/polyaniline extraction to prepare the method for solid-carrying type phosphorus heteropoly tungstic acid.This method solve routine to prepare and use a large amount of extracted with diethyl ether in heteropoly acid process and cause the problem such as the wasting of resources and air ambient pollution.
the present invention prepares the scheme that supported heteropolyacid takes:
1, ether/polyaniline extractant preparation
After adopting chemical oxidization method to prepare carrier polyaniline, then infusion process or absorption method is adopted to obtain ether/polyaniline extractant.
2, solid-carrying type phosphorus heteropoly tungstic acid preparation
To in sodium tungstate and the sodium hydrogen phosphate aqueous solution, uniform temperature, drips hydrochloric acid, controls reaction temperature, acid adding amount, ensures that reaction terminates rear without crystal generation, obtained phosphorus heteropoly tungstic acid reactant liquor.
Again reactant liquor is cooled to room temperature, adds appropriate hydrochloric acid and ether/polyaniline extractant successively, stir, leave standstill, suction filtration, dry, dry, obtain solid-carrying type phosphorus heteropoly tungstic acid.
Heteropoly acid in ether/polyaniline extractant extractive reaction liquid can be used by method of the present invention; not only can simplify solid-carrying type phosphorus heteropoly tungstic acid preparation flow; it also avoid conventional method to prepare when extracting in phosphorus heteropoly tungstic acid process and use ether in a large number simultaneously; and cause the problems such as waste and difficult recycling, have environmental protection meaning simultaneously.
Accompanying drawing explanation
Fig. 1 is that the present invention prepares supported heteropolyacid flow chart.
Detailed description of the invention
Concrete process according to Fig. 1 prepares supported heteropolyacid.
1, ether/polyaniline extractant preparation
Prepared by polyaniline in eigenstate (PANI): in there-necked flask, pour the 1.0mol/L hydrochloric acid 160mL being dissolved with 15g aniline into.Under agitation, the 1.0mol/L hydrochloric acid 160mL being dissolved with 36.5g ammonium persulfate is slowly dripped.Front 4h maintains the temperature at (mixture of ice and water cooling) between 5-15 DEG C, then room temperature reaction 20h.Suction filtration, the BaCl of mass fraction 2% extremely used by filter cake with 1.0mol/L salt acid elution
2aqueous solution inspection is without SO
4 2-till, more repeatedly washing to filtrate colourless with 200mL acetone, suction filtration, filter cake, in 60 DEG C of vacuum drying 48h, obtains cyan doped hydrochloride state polyaniline (HCl/PANI).HCl/PANI, through the ammonia spirit of mass fraction 10%, soaks 12h contra-doping and obtains bolarious polyaniline in eigenstate (PANI) after stirring.
Ether/polyaniline extractant preparation: the ether/polyaniline extractant adopting infusion process or absorption legal system, for subsequent use.
(1) infusion process
Adopt general dipping method, getting a certain amount of polyaniline in eigenstate (PANI) places in conical flask, add a certain amount of ether in conical flask, make the polyaniline (PANI) that ether just submergence adds, sealing, constant temperature, regularly, air purges sample, naturally dries, for subsequent use.
(2) absorption method
A certain amount of ether is put into 200mL flask, adds a certain amount of polyaniline in eigenstate wherein, then add hot reflux, and constantly stir, after reaction a period of time, take out, air purges sample, naturally dries, for subsequent use.
2, supported heteropolyacid preparation
25g sodium tungstate and 4g sodium hydrogen phosphate are put in the there-necked flask of 250ml, add 60ml water, add thermal agitation, treat that two reactants dissolve completely and rise to uniform temperature, slowly drip a certain amount of hydrochloric acid, control reaction temperature (<80 DEG C) and acid adding amount (<14ml) in the process, thus ensure that reaction terminates to generate without crystal afterwards.After reaction terminates, question response liquid is cooled to room temperature, after adding appropriate hydrochloric acid, observes solution colour change, then to add diethyl ether/polyaniline extractant extracts; In there-necked flask, stir after a period of time, suction filtration, is placed in surface plate, naturally dries, and obtains Polyaniline-Supported type phosphorus heteropoly tungstic acid solid catalyst, then in vacuum drying chamber 50 DEG C be dried to constant weight, namely obtain product solid-carrying type phosphorus heteropoly tungstic acid.
3, the test of supported heteropolyacid catalytic performance
The supported heteropolyacid catalyst preparing gained in 2 is carried out in different esterification system the test of catalytic performance, result is as shown in the table,
Record its catalytic effect good, higher esterification yield can be obtained.
Claims (5)
1. in order to improve the preparation technology of supported heteropolyacid, the present invention proposes to utilize ether/polyaniline extraction phosphorus heteropoly tungstic acid to prepare the method for solid-carrying type phosphorus heteropoly tungstic acid, this method solves routine and prepares and use a large amount of extracted with diethyl ether in heteropoly acid process and cause the problem such as the wasting of resources and environmental pollution.
2. the preparation method of this solid-carrying type phosphorus heteropoly tungstic acid comprises:
Ether/polyaniline extractant preparation
After adopting chemical oxidization method to prepare carrier polyaniline, then infusion process or absorption method is adopted to obtain ether/polyaniline extractant.
3. solid-carrying type phosphorus heteropoly tungstic acid preparation
To in sodium tungstate and the sodium hydrogen phosphate aqueous solution, uniform temperature, drips hydrochloric acid, controls reaction temperature, acid adding amount, ensures that reaction terminates rear without crystal generation, obtained phosphorus heteropoly tungstic acid solution.
4. again reactant liquor is cooled to room temperature, adds appropriate hydrochloric acid and ether/polyaniline extractant successively, stir, leave standstill, suction filtration, dry, dry, obtain solid-carrying type phosphorus heteropoly tungstic acid.
5. can use phosphorus heteropoly tungstic acid in ether/polyaniline extractant extractive reaction liquid by method of the present invention; not only can simplify solid-carrying type phosphorus heteropoly tungstic acid preparation flow; it also avoid conventional method to prepare when extracting in phosphorus heteropoly tungstic acid process and use ether in a large number simultaneously; and cause the problems such as waste and difficult recycling, simultaneously meaningful to protection of the environment.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126890A (en) * | 2018-08-23 | 2019-01-04 | 江苏扬农化工集团有限公司 | A kind of preparation method of the olefin epoxidation catalysts of Polyaniline-Supported heteropoly acid |
| RU2728346C1 (en) * | 2016-08-26 | 2020-07-29 | Сентрал Сауф Юниверсити | Method of producing phosphotungstic acid |
| CN112742454A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of supported heteropolyacid catalyst |
| CN113398987A (en) * | 2020-03-16 | 2021-09-17 | 南京工业大学 | Heteropolyacid composite catalyst material H3PW12O40PAN and preparation method and application thereof |
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| CN102659181A (en) * | 2012-05-08 | 2012-09-12 | 中南大学 | Method for preparing phosphotungstic heteropoly acid with Keggin structure |
| CN102744088A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Preparation method of silicotungstic heteropoly acid |
| CN103613082A (en) * | 2013-11-15 | 2014-03-05 | 中南大学 | Method for preparing Dawson heteropolyphosphatotungstate |
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Patent Citations (4)
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| CN102074375A (en) * | 2011-01-02 | 2011-05-25 | 桂林理工大学 | Preparation method for high-cyclical-stability composite capacitor material |
| CN102744088A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Preparation method of silicotungstic heteropoly acid |
| CN102659181A (en) * | 2012-05-08 | 2012-09-12 | 中南大学 | Method for preparing phosphotungstic heteropoly acid with Keggin structure |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2728346C1 (en) * | 2016-08-26 | 2020-07-29 | Сентрал Сауф Юниверсити | Method of producing phosphotungstic acid |
| CN109126890A (en) * | 2018-08-23 | 2019-01-04 | 江苏扬农化工集团有限公司 | A kind of preparation method of the olefin epoxidation catalysts of Polyaniline-Supported heteropoly acid |
| CN109126890B (en) * | 2018-08-23 | 2021-06-25 | 江苏扬农化工集团有限公司 | Preparation method of olefin epoxidation catalyst of polyaniline-loaded heteropoly acid |
| CN112742454A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of supported heteropolyacid catalyst |
| CN112742454B (en) * | 2019-10-31 | 2022-08-12 | 中国石油化工股份有限公司 | Preparation method of supported heteropoly acid catalyst |
| CN113398987A (en) * | 2020-03-16 | 2021-09-17 | 南京工业大学 | Heteropolyacid composite catalyst material H3PW12O40PAN and preparation method and application thereof |
| CN113398987B (en) * | 2020-03-16 | 2022-08-23 | 南京工业大学 | Heteropolyacid composite catalyst material H 3 PW 12 O 40 PAN and preparation method and application thereof |
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