CN107954847A - The method of silicon dioxide carried Catalyzed by Phosphotungstic Acid synthesis 1,3- dichloroacetones - Google Patents
The method of silicon dioxide carried Catalyzed by Phosphotungstic Acid synthesis 1,3- dichloroacetones Download PDFInfo
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- CN107954847A CN107954847A CN201711141195.1A CN201711141195A CN107954847A CN 107954847 A CN107954847 A CN 107954847A CN 201711141195 A CN201711141195 A CN 201711141195A CN 107954847 A CN107954847 A CN 107954847A
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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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/294—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with hydrogen peroxide
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Abstract
The present invention discloses a kind of method that silicon dioxide carried Catalyzed by Phosphotungstic Acid synthesizes 1,3 dichloroacetones, comprises the following steps：（1）Disodium tungstate (Na2WO4) dihydrate is soluble in water, under stirring, phosphoric acid is added dropwise into system, flows back again after being added dropwise；（2）Natural cooling crystallization, crystal is re-dissolved in 80 DEG C of water, is then added ether extraction, is recrystallized in water, obtain phosphorus heteropoly tungstic acid；（3）Ethyl orthosilicate, deionized water, absolute ethyl alcohol, phosphorus heteropoly tungstic acid heteropoly acid are mixed, stirring, form gel, then still aging again, drying, obtains obtaining silicon dioxide carried phosphorus heteropoly tungstic acid catalyzer；（4）1,3 dichlorohydrin is mixed with hydrogenperoxide steam generator, adds silicon dioxide carried phosphorus heteropoly tungstic acid catalyzer, isothermal reaction 10h, filtering, filtrate is 1,3 dichloroacetones.Method provided by the invention, easy to operate, environmental pollution is few, and high income, the purity of 1,3 dichloroacetone are good.
Description
Technical field
The invention belongs to the preparation method of 1,3-DCA, and in particular to a kind of silicon dioxide carried phosphorus heteropoly tungstic acid is urged
It is combined to the method for 1,3- dichloroacetones.
Background technology
1,3-DCA has two kinds of active function groups of carbonyl and halogen atom at the same time, is a kind of important chemical industry and medicine
The reaction intermediate of industry.
At present, the synthetic method of 1,3-DCA has：（1）Substitution reaction, the method are directly occurred with chlorine using acetone
Reaction speed not easy to control, can largely generate 1,1- dichloroacetones and 1, and 1,3- trichloroacetone, separation is difficult, and to corrosion of equipment
Seriously；（2）With 1,3- dichlorohydrins for raw material, 1,3- chlorine is prepared with chromium trioxide-sulfuric acid or sodium dichromate-concentrated sulfuric acid oxidizing process
Acetone, the method high income, catalyst chromium is seriously polluted, to equipment requirement height.Solve the key of 1,3-DCA composition problem
It is the selection of catalyst, green catalyst heteropoly acid becomes the preferred catalyst of research at present.
Heteropoly acid has very high catalytic activity, is a kind of Bronsted acid of even intensity, anti-available for esterification, dehydration
Should be with numerous aspects such as redox reaction.But the specific surface area of heteropoly acid it is small (<10m2/ g), polar solvent is soluble in, is recycled
Difficulty, the application in terms of catalysis are restricted.
The content of the invention
The defects of for the prior art, the present invention provide a kind of silicon dioxide carried Catalyzed by Phosphotungstic Acid synthesis 1,3- bis-
The method of chlroacetone.
The method of silicon dioxide carried Catalyzed by Phosphotungstic Acid synthesis 1,3-DCA, comprises the following steps：
（1）Disodium tungstate (Na2WO4) dihydrate is dissolved in 40-50 DEG C of water, under stirring, phosphoric acid is added dropwise into system, is added dropwise
Flow back at 80 DEG C 6-8h again afterwards；
（2）By step（1）Product natural cooling crystallization, crystal is re-dissolved in 80 DEG C of water, then add ether extraction,
Recrystallized in water, obtain phosphorus heteropoly tungstic acid；
（3）By ethyl orthosilicate, deionized water, absolute ethyl alcohol, phosphorus heteropoly tungstic acid heteropoly acid according to mass ratio 14：（25-35）：
（20-25）：（0.45-3.3）Mixing, is stirred at 55-60 DEG C, forms gel, and then in still aging 24h, drying, obtains
Silicon dioxide carried phosphorus heteropoly tungstic acid catalyzer；
（4）1,3- dichlorohydrins are mixed with hydrogenperoxide steam generator, add step（3）Obtained silicon dioxide carried phosphorus tungsten is miscellaneous more
Acid catalyst, the isothermal reaction 10h at 50-70 DEG C, is recovered by filtration silicon dioxide carried phosphorus heteropoly tungstic acid catalyzer, and filtrate is
1,3- dichloroacetones.
Preferably, step（1）Middle Disodium tungstate (Na2WO4) dihydrate, water, the mass ratio of phosphoric acid are 3:20:2.
Preferably, step（3）The condition of middle drying is that 4h is dried under conditions of 140-150 DEG C.
Preferably, step（4）The mass concentration of middle hydrogenperoxide steam generator is 30%.
Preferably, step（4）In 1,3- dichlorohydrins, hydrogenperoxide steam generator, silicon dioxide carried Catalyzed by Phosphotungstic Acid
The mass ratio of agent is 10:9:0.08.
Advantages of the present invention：
Method provided by the invention using silicon dioxide carried Catalyzed by Phosphotungstic Acid synthesis 1,3-DCA, operation letter
Single, environmental pollution is few, environmentally protective, and the catalyst reusing of preparation is high, high income, the purity of 1,3-DCA
It is good.
Embodiment
Embodiment 1
The method of silicon dioxide carried Catalyzed by Phosphotungstic Acid synthesis 1,3-DCA, comprises the following steps：
（1）Disodium tungstate (Na2WO4) dihydrate is dissolved in 40 DEG C of water, under stirring, phosphoric acid is added dropwise into system, after being added dropwise
Flow back at 80 DEG C 6h again；Wherein, Disodium tungstate (Na2WO4) dihydrate, water, the mass ratio of phosphoric acid are 3:20:2；
（2）By step（1）Product natural cooling crystallization, crystal is re-dissolved in 80 DEG C of water, then add ether extraction,
Recrystallized in water, obtain phosphorus heteropoly tungstic acid；
（3）By ethyl orthosilicate, deionized water, absolute ethyl alcohol, phosphorus heteropoly tungstic acid heteropoly acid according to mass ratio 14：25：20：0.45
Mixing, is stirred at 55 DEG C, forms gel, then in still aging 24h, 4h is dried under conditions of 140 DEG C, obtains obtaining dioxy
SiClx loads phosphorus heteropoly tungstic acid catalyzer；
（4）1,3- dichlorohydrins are mixed with the hydrogenperoxide steam generator that mass concentration is 30%, add step（3）Obtained dioxy
SiClx loads phosphorus heteropoly tungstic acid catalyzer, wherein, 1,3- dichlorohydrin, hydrogenperoxide steam generator, silicon dioxide carried phosphorus tungsten are miscellaneous more
The mass ratio of acid catalyst is 10:9:0.08, the isothermal reaction 10h at 50 DEG C, it is miscellaneous more to be recovered by filtration silicon dioxide carried phosphorus tungsten
Acid catalyst, filtrate are 1,3-DCA.
Embodiment 2
The method of silicon dioxide carried Catalyzed by Phosphotungstic Acid synthesis 1,3-DCA, comprises the following steps：
（1）Disodium tungstate (Na2WO4) dihydrate is dissolved in 50 DEG C of water, under stirring, phosphoric acid is added dropwise into system, after being added dropwise
Flow back at 80 DEG C 8h again；Wherein, Disodium tungstate (Na2WO4) dihydrate, water, the mass ratio of phosphoric acid are 3:20:2；
（2）By step（1）Product natural cooling crystallization, crystal is re-dissolved in 80 DEG C of water, then add ether extraction,
Recrystallized in water, obtain phosphorus heteropoly tungstic acid；
（3）By ethyl orthosilicate, deionized water, absolute ethyl alcohol, phosphorus heteropoly tungstic acid heteropoly acid according to mass ratio 14：35：25：3.3
Mixing, is stirred at 60 DEG C, forms gel, then in still aging 24h, 4h is dried under conditions of 150 DEG C, obtains obtaining dioxy
SiClx loads phosphorus heteropoly tungstic acid catalyzer；
（4）1,3- dichlorohydrins are mixed with the hydrogenperoxide steam generator that mass concentration is 30%, add step（3）Obtained dioxy
SiClx loads phosphorus heteropoly tungstic acid catalyzer, wherein, 1,3- dichlorohydrin, hydrogenperoxide steam generator, silicon dioxide carried phosphorus tungsten are miscellaneous more
The mass ratio of acid catalyst is 10:9:0.08, the isothermal reaction 10h at 70 DEG C, it is miscellaneous more to be recovered by filtration silicon dioxide carried phosphorus tungsten
Acid catalyst, filtrate are 1,3-DCA.
Embodiment 3
The method of silicon dioxide carried Catalyzed by Phosphotungstic Acid synthesis 1,3-DCA, comprises the following steps：
（1）Disodium tungstate (Na2WO4) dihydrate is dissolved in 45 DEG C of water, under stirring, phosphoric acid is added dropwise into system, after being added dropwise
Flow back at 80 DEG C 7h again；Wherein, Disodium tungstate (Na2WO4) dihydrate, water, the mass ratio of phosphoric acid are 3:20:2；
（2）By step（1）Product natural cooling crystallization, crystal is re-dissolved in 80 DEG C of water, then add ether extraction,
Recrystallized in water, obtain phosphorus heteropoly tungstic acid；
（3）By ethyl orthosilicate, deionized water, absolute ethyl alcohol, phosphorus heteropoly tungstic acid heteropoly acid according to mass ratio 14：30：22：2.2
Mixing, is stirred at 58 DEG C, forms gel, then in still aging 24h, 4h is dried under conditions of 145 DEG C, obtains obtaining dioxy
SiClx loads phosphorus heteropoly tungstic acid catalyzer；
（4）1,3- dichlorohydrins are mixed with the hydrogenperoxide steam generator that mass concentration is 30%, add step（3）Obtained dioxy
SiClx loads phosphorus heteropoly tungstic acid catalyzer, wherein, 1,3- dichlorohydrin, hydrogenperoxide steam generator, silicon dioxide carried phosphorus tungsten are miscellaneous more
The mass ratio of acid catalyst is 10:9:0.08, the isothermal reaction 10h at 60 DEG C, it is miscellaneous more to be recovered by filtration silicon dioxide carried phosphorus tungsten
Acid catalyst, filtrate are 1,3-DCA.
Claims (5)
1. the method for silicon dioxide carried Catalyzed by Phosphotungstic Acid synthesis 1,3-DCA, it is characterised in that：Including following step
Suddenly：
（1）Disodium tungstate (Na2WO4) dihydrate is dissolved in 40-50 DEG C of water, under stirring, phosphoric acid is added dropwise into system, is added dropwise
Flow back at 80 DEG C 6-8h again afterwards；
（2）By step（1）Product natural cooling crystallization, crystal is re-dissolved in 80 DEG C of water, then add ether extraction,
Recrystallized in water, obtain phosphorus heteropoly tungstic acid；
（3）By ethyl orthosilicate, deionized water, absolute ethyl alcohol, phosphorus heteropoly tungstic acid heteropoly acid according to mass ratio 14：（25-35）：
（20-25）：（0.45-3.3）Mixing, is stirred at 55-60 DEG C, forms gel, and then in still aging 24h, drying, obtains
Silicon dioxide carried phosphorus heteropoly tungstic acid catalyzer；
（4）1,3- dichlorohydrins are mixed with hydrogenperoxide steam generator, add step（3）Obtained silicon dioxide carried phosphorus tungsten is miscellaneous more
Acid catalyst, the isothermal reaction 10h at 50-70 DEG C, is recovered by filtration silicon dioxide carried phosphorus heteropoly tungstic acid catalyzer, and filtrate is
1,3- dichloroacetones.
2. the method for silicon dioxide carried Catalyzed by Phosphotungstic Acid synthesis 1,3-DCA according to claim 1, it is special
Sign is：Step（1）Middle Disodium tungstate (Na2WO4) dihydrate, water, the mass ratio of phosphoric acid are 3:20:2.
3. the method for silicon dioxide carried Catalyzed by Phosphotungstic Acid synthesis 1,3-DCA according to claim 1, it is special
Sign is：Step（3）The condition of middle drying is that 4h is dried under conditions of 140-150 DEG C.
4. the method for silicon dioxide carried Catalyzed by Phosphotungstic Acid synthesis 1,3-DCA according to claim 1, it is special
Sign is：Step（4）The mass concentration of middle hydrogenperoxide steam generator is 30%.
5. the method for silicon dioxide carried Catalyzed by Phosphotungstic Acid synthesis 1,3-DCA according to claim 1, it is special
Sign is：Step（4）In 1,3- dichlorohydrins, hydrogenperoxide steam generator, the quality of silicon dioxide carried phosphorus heteropoly tungstic acid catalyzer
Than for 10:9:0.08.
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| CN201711141195.1A CN107954847A (en) | 2017-11-17 | 2017-11-17 | The method of silicon dioxide carried Catalyzed by Phosphotungstic Acid synthesis 1,3- dichloroacetones |
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| CN201711141195.1A CN107954847A (en) | 2017-11-17 | 2017-11-17 | The method of silicon dioxide carried Catalyzed by Phosphotungstic Acid synthesis 1,3- dichloroacetones |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110801865A (en) * | 2019-11-19 | 2020-02-18 | 滁州学院 | Preparation method of impurity-free Preyssler type heteropoly acid |
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2017
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110801865A (en) * | 2019-11-19 | 2020-02-18 | 滁州学院 | Preparation method of impurity-free Preyssler type heteropoly acid |
| CN110801865B (en) * | 2019-11-19 | 2022-07-22 | 滁州学院 | Preparation method of impurity-free Preyssler type heteropoly acid |
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Application publication date: 20180424 |
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