CN110479374A - A kind of phosphorus heteropoly tungstic acid salt catalyst and preparation method thereof for synthesizing epoxy chloropropane - Google Patents
A kind of phosphorus heteropoly tungstic acid salt catalyst and preparation method thereof for synthesizing epoxy chloropropane Download PDFInfo
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- CN110479374A CN110479374A CN201910890752.2A CN201910890752A CN110479374A CN 110479374 A CN110479374 A CN 110479374A CN 201910890752 A CN201910890752 A CN 201910890752A CN 110479374 A CN110479374 A CN 110479374A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
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Abstract
The invention discloses a kind of preparation methods of temperature control phase transfer catalyst for synthesizing epoxy chloropropane, belong to field of catalytic chemistry.Specific synthetic method are as follows: K-type phosphotungstic acid is dissolved in oxidation reaction in 30% hydrogen peroxide and obtains peroxide phosphotungstic acid aqueous solution, then peroxide phosphotungstic acid aqueous solution is added drop-wise in the ethanol solution of dimethyldioctadecylammonium ammonium chloride, 2 h is stirred to react under the conditions of 40 DEG C.White powder is filtered to obtain after reaction, and by washing, dehydrated alcohol is washed, and is dried in vacuo, and dimethyldioctadecylammonium base peroxide phosphotungstic acid catalyst is obtained.Using dimethyldioctadecylammonium base peroxide phosphotungstic acid as catalyst, using chloropropene, hydrogen peroxide as raw material, in the case where solvent-free and auxiliary agent, reach 97.1% by the yield that one kettle way prepares epoxychloropropane, selectivity is greater than 99%, and product yield is up to 96% or more.The catalyst is dissolved in epoxychloropropane after reaction, and catalyst is precipitated when cooling to 10 DEG C, and the recycling of catalyst is realized by filtration method.The catalysis reaction process is easy to operate, and reaction condition is mild, and production cost is low, and catalyst property is stable and recycles conveniently, is conducive to industrialized production.
Description
Technical field
The present invention relates to field of catalytic chemistry, specifically about a kind of phospho heteropoly tungstate for synthesizing epoxy chloropropane
Catalyst and preparation method thereof.
Background technique
Epoxychloropropane is a kind of important organic synthesis intermediate and fine chemical product, the epoxy chloropropionate in the whole world 85%
Alkane is used to produce epoxy resin, and China is the maximum producing country of epoxy resin and country of consumption.Propylene high-temperature chloridising and acetic acid third
Enester method is to produce the main technique of epoxychloropropane at this stage, although both methods is mature, stable operation can not all be kept away
The generation waste water exempted from, and production energy consumption is high, severe corrosion to equipment.Therefore, a kind of simple, efficiently, green epoxy is developed
Chloropropane synthesis technology is significant.
Hydrogen peroxide is widely used in the epoxidation research of alkene as a kind of green oxygen source.Japanese Laid-Open Patent Publication 4-5028
It reports in bulletin and patent CN1639143A using titan silicate as catalyst, carries out epoxidation of propylene using hydrogen peroxide and synthesize ring
The method of oxygen chloropropane.Titanosilicate catalyst preparation cost is relatively high, and technique is not mature enough, and in known production method
In cannot get enough catalytic activity.A kind of use is reported in 101205219 B of patent CN and cleans oxygen source-hydrogen peroxide, anti-
It should control and directly react the reaction process for preparing propylene oxide with propylene under the action of phase transfer catalyst.However, catalysis reaction
Additional organic solvent and phosphate builder are used in system, and the conversion ratio of propylene only has 93%.Similarly, patent
CN100575349C report has excessive chloropropene in phosphate-tungstic acid and co-catalyst alkyl phenol polyoxyethylene ether
Under, epoxychloropropane is directly generated by oxidant of hydrogen peroxide, uses excessive chloropropene and organic additive in reaction process,
It is unfavorable for industrialized production.
Under the situation that environmental requirement is increasingly stringenter, realize that green production becomes the target of enterprise development.It is anti-in catalysis
It answers in system, prepares one kind simply, efficiently, the catalyst easily recycled is most important.
Summary of the invention
The present invention provides a kind of raw catelyst dimethyl for deficiency present in existing synthesizing epoxy chloropropane technique
The synthetic method of double octadecyl peroxide phosphotungstic acids.This method is simple and easy, and reaction condition is mild, it is raw materials used safely, be easy to get,
It is convenient for industrialized production.Using hydrogen peroxide as oxygen source, without other organic solvents and in the case where auxiliary agent, dimethyldioctadecylammonium base
Peroxide phosphotungstic acid can directly be catalyzed chloropropene synthesizing epoxy chloropropane.
The present invention is achieved by the following technical solutions:
Phosphotungstic acid is easily soluble in hydrogen peroxide, and hydrogen peroxide can aoxidize phosphotungstic acid to obtain peroxide Salkowski's solution at room temperature.
Dimethyldioctadecylammonium ammonium chloride is soluble in dehydrated alcohol, and under the conditions of 40 DEG C, peroxide Salkowski's solution is added drop-wise to dimethyl
In the ethanol solution of double octadecyl ammonium chlorides, dimethyldioctadecylammonium base peroxide phosphotungstic acid solid can be obtained.Isothermal reaction 2
H makes reaction more abundant.Catalyst crude product is obtained by filtering, by washing, ethyl alcohol is washed, will a small amount of unreacted reactant
It washes off, obtains pure compound.
Beneficial effect
During the dimethyldioctadecylammonium base peroxide catalysis of phosphotungstic acid epoxidation chloropropene that the present invention synthesizes, others are not needed
The molar ratio of organic solvent and auxiliary agent, chloropropene and hydrogen peroxide is 1:1, and the high conversion rate of epoxychloropropane is selective up to 97.1%
Greater than 99%, yield 96%.The catalyst, which belongs to temperature control phase transfer catalyst, reduces temperature catalyst after reaction
It is precipitated, is recovered by filtration.Catalyst still has relatively high catalytic activity after circulation 7 times, and selectivity is good, reacts acquisition
Epoxychloropropane high income.
In conclusion the catalyst that the present invention synthesizes is for being catalyzed chloropropene synthesizing epoxy chloropropane, technological operation is simple,
Reaction condition is mild, and production cost is low, catalyst recycling is convenient, therefore is more conducive to industrialized implementation.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, and the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as the limit to range
It is fixed.Fig. 1 is the infrared spectrogram for the dimethyldioctadecylammonium base peroxide phosphotungstic acid that the embodiment of the present invention 1 provides.1090 cm-1For
PO4 3-In P-O key absorption peak, 976 cm-1For the absorption peak of W=O key, 846 cm-1For the absorption peak of O-O key, 787,
727、657 cm-1For the absorption peak of cation.
Specific embodiment
Following examples are not construed as limiting the invention to the further explanation of substantive content of the present invention.The present invention
Raw material used can be bought in the market.
Embodiment 1
1.152 kg phosphotungstic acid solids, the hydrogen peroxide of 1.7 L 30% are added in the glass reaction kettle of 5 L, room temperature is protected from light stirring
Reaction.0.727 kg of dimethyldioctadecylammonium ammonium chloride, 8 L of dehydrated alcohol are added to the glass reaction kettle of 50 L simultaneously
In, 40 DEG C of heating for dissolving.The peroxide Salkowski's solution obtained in the glass reaction kettle of 5 L is added drop-wise to 50 with metering pump after 2 h
In the glass reaction kettle of L, after completion of dropwise addition, 40 DEG C are continued to be stirred to react 2 h.After reaction, it is cooled to room temperature, depressurized
Filter, obtains catalyst white powder crude product, by the distillation water washing of 40 L of white powder, then with the ethanol washing of 10 L, filters,
40 DEG C of 6 h of vacuum drying obtain white catalyst powder and amount to 1.776 kg.
Embodiment 2
1.152 kg phosphotungstic acid solids, the hydrogen peroxide of 1.7 L 30% are added in the glass reaction kettle of 5 L, room temperature is protected from light stirring
Reaction.0.727 kg of dimethyldioctadecylammonium ammonium chloride, 8 L of dehydrated alcohol are added to the glass reaction kettle of 50 L simultaneously
In, 45 DEG C of heating for dissolving.The peroxide Salkowski's solution obtained in the glass reaction kettle of 5 L is added drop-wise to 50 with metering pump after 2 h
In the glass reaction kettle of L, after completion of dropwise addition, 45 DEG C are continued to be stirred to react 2 h.After reaction, it is cooled to room temperature, depressurized
Filter, obtains catalyst white powder crude product, by the distillation water washing of 40 L of white powder, then with the ethanol washing of 10 L, filters,
40 DEG C of 6 h of vacuum drying obtain white catalyst powder and amount to 1.764 kg.
Embodiment 3
1.152 kg phosphotungstic acid solids, the hydrogen peroxide of 1.7 L 30% are added in the glass reaction kettle of 5 L, room temperature is protected from light stirring
Reaction.0.727 kg of dimethyldioctadecylammonium ammonium chloride, 8 L of dehydrated alcohol are added to the glass reaction kettle of 50 L simultaneously
In, 50 DEG C of heating for dissolving.The peroxide Salkowski's solution obtained in the glass reaction kettle of 5 L is added drop-wise to 50 with metering pump after 2 h
In the glass reaction kettle of L, after completion of dropwise addition, 50 DEG C are continued to be stirred to react 2 h.After reaction, it is cooled to room temperature, depressurized
Filter, obtains catalyst white powder crude product, by the distillation water washing of 40 L of white powder, then with the ethanol washing of 10 L, filters,
40 DEG C of 6 h of vacuum drying obtain white catalyst powder and amount to 1.730 kg.
Embodiment 4
1.152 kg phosphotungstic acid solids, the hydrogen peroxide of 1.7 L 30% are added in the glass reaction kettle of 5 L, room temperature is protected from light stirring
Reaction.0.727 kg of dimethyldioctadecylammonium ammonium chloride, 8 L of dehydrated alcohol are added to the glass reaction kettle of 50 L simultaneously
In, 55 DEG C of heating for dissolving.The peroxide Salkowski's solution obtained in the glass reaction kettle of 5 L is added drop-wise to 50 with metering pump after 2 h
In the glass reaction kettle of L, after completion of dropwise addition, 55 DEG C are continued to be stirred to react 2 h.After reaction, it is cooled to room temperature, depressurized
Filter, obtains catalyst white powder crude product, by the distillation water washing of 40 L of white powder, then with the ethanol washing of 10 L, filters,
40 DEG C of 6 h of vacuum drying obtain white catalyst powder and amount to 1.725 kg.
Embodiment 5
1.152 kg phosphotungstic acid solids, the hydrogen peroxide of 1.7 L 30% are added in the glass reaction kettle of 5 L, room temperature is protected from light stirring
Reaction.0.727 kg of dimethyldioctadecylammonium ammonium chloride, 8 L of dehydrated alcohol are added to the glass reaction kettle of 50 L simultaneously
In, 60 DEG C of heating for dissolving.The peroxide Salkowski's solution obtained in the glass reaction kettle of 5 L is added drop-wise to 50 with metering pump after 2 h
In the glass reaction kettle of L, after completion of dropwise addition, 60 DEG C are continued to be stirred to react 2 h.After reaction, it is cooled to room temperature, depressurized
Filter, obtains catalyst white powder crude product, by the distillation water washing of 40 L of white powder, then with the ethanol washing of 10 L, filters,
40 DEG C of 6 h of vacuum drying obtain white catalyst powder and amount to 1.718 kg.
Embodiment 6
1.152 kg phosphotungstic acid solids, the hydrogen peroxide of 1.5 L 30% are added in the glass reaction kettle of 5 L, room temperature is protected from light stirring
Reaction.0.727 kg of dimethyldioctadecylammonium ammonium chloride, 8 L of dehydrated alcohol are added to the glass reaction kettle of 50 L simultaneously
In, 40 DEG C of heating for dissolving.The peroxide Salkowski's solution obtained in the glass reaction kettle of 5 L is added drop-wise to 50 with metering pump after 2 h
In the glass reaction kettle of L, after completion of dropwise addition, 40 DEG C are continued to be stirred to react 2 h.After reaction, it is cooled to room temperature, depressurized
Filter, obtains catalyst white powder crude product, by the distillation water washing of 40 L of white powder, then with the ethanol washing of 10 L, filters,
40 DEG C of 6 h of vacuum drying obtain white catalyst powder and amount to 1.770 kg.
Embodiment 7
1.152 kg phosphotungstic acid solids, the hydrogen peroxide of 1.3 L 30% are added in the glass reaction kettle of 5 L, room temperature is protected from light stirring
Reaction.0.727 kg of dimethyldioctadecylammonium ammonium chloride, 8 L of dehydrated alcohol are added to the glass reaction kettle of 50 L simultaneously
In, 40 DEG C of heating for dissolving.The peroxide Salkowski's solution obtained in the glass reaction kettle of 5 L is added drop-wise to 50 with metering pump after 2 h
In the glass reaction kettle of L, after completion of dropwise addition, 40 DEG C are continued to be stirred to react 2 h.After reaction, it is cooled to room temperature, depressurized
Filter, obtains catalyst white powder crude product, by the distillation water washing of 40 L of white powder, then with the ethanol washing of 10 L, filters,
40 DEG C of 6 h of vacuum drying obtain white catalyst powder and amount to 1.761 kg.
Embodiment 8
1.152 kg phosphotungstic acid solids, the hydrogen peroxide of 1.1 L 30% are added in the glass reaction kettle of 5 L, room temperature is protected from light stirring
Reaction.0.727 kg of dimethyldioctadecylammonium ammonium chloride, 8 L of dehydrated alcohol are added to the glass reaction kettle of 50 L simultaneously
In, 40 DEG C of heating for dissolving.The peroxide Salkowski's solution obtained in the glass reaction kettle of 5 L is added drop-wise to 50 with metering pump after 2 h
In the glass reaction kettle of L, after completion of dropwise addition, 40 DEG C are continued to be stirred to react 2 h.After reaction, it is cooled to room temperature, depressurized
Filter, obtains catalyst white powder crude product, by the distillation water washing of 40 L of white powder, then with the ethanol washing of 10 L, filters,
40 DEG C of 6 h of vacuum drying obtain white catalyst powder and amount to 1.750kg.
Embodiment 9
1.152 kg phosphotungstic acid solids, the hydrogen peroxide of 1.0 L 30% are added in the glass reaction kettle of 5 L, room temperature is protected from light stirring
Reaction.0.727 kg of dimethyldioctadecylammonium ammonium chloride, 8 L of dehydrated alcohol are added to the glass reaction kettle of 50 L simultaneously
In, 40 DEG C of heating for dissolving.The peroxide Salkowski's solution obtained in the glass reaction kettle of 5 L is added drop-wise to 50 with metering pump after 2 h
In the glass reaction kettle of L, after completion of dropwise addition, 40 DEG C are continued to be stirred to react 2 h.After reaction, it is cooled to room temperature, depressurized
Filter, obtains catalyst white powder crude product, by the distillation water washing of 40 L of white powder, then with the ethanol washing of 10 L, filters,
40 DEG C of 6 h of vacuum drying obtain white catalyst powder and amount to 1.745 kg.
Embodiment 10
1.152 kg phosphotungstic acid solids, the hydrogen peroxide of 0.9 L 30% are added in the glass reaction kettle of 5 L, room temperature is protected from light stirring
Reaction.0.727 kg of dimethyldioctadecylammonium ammonium chloride, 8 L of dehydrated alcohol are added to the glass reaction kettle of 50 L simultaneously
In, 40 DEG C of heating for dissolving.The peroxide Salkowski's solution obtained in the glass reaction kettle of 5 L is added drop-wise to 50 with metering pump after 2 h
In the glass reaction kettle of L, after completion of dropwise addition, 40 DEG C are continued to be stirred to react 2 h.After reaction, it is cooled to room temperature, depressurized
Filter, obtains catalyst white powder crude product, by the distillation water washing of 40 L of white powder, then with the ethanol washing of 10 L, filters,
40 DEG C of 6 h of vacuum drying obtain white catalyst powder and amount to 1.740 kg.
Embodiment 11
1.152 kg phosphotungstic acid solids, the hydrogen peroxide of 0.85 L 30% are added in the glass reaction kettle of 5 L, room temperature is protected from light stirring
Reaction.0.727 kg of dimethyldioctadecylammonium ammonium chloride, 8 L of dehydrated alcohol are added to the glass reaction kettle of 50 L simultaneously
In, 40 DEG C of heating for dissolving.The peroxide Salkowski's solution obtained in the glass reaction kettle of 5 L is added drop-wise to 50 with metering pump after 2 h
In the glass reaction kettle of L, after completion of dropwise addition, 40 DEG C are continued to be stirred to react 2 h.After reaction, it is cooled to room temperature, depressurized
Filter, obtains catalyst white powder crude product, by the distillation water washing of 40 L of white powder, then with the ethanol washing of 10 L, filters,
40 DEG C of 6 h of vacuum drying obtain white catalyst powder and amount to 1.731 kg.
Application examples 12
454 g, 30% hydrogen peroxide, 306 g chloropropenes and embodiment 1 are added in the glass reaction kettle of 5 L to embodiment 11
Obtained in 53.4 g of catalyst.Mixed liquor is reacted into 6 h at 55 DEG C, cooling, (epoxychloropropane of generation exists for liquid separation
Lower layer), by gas chromatographic detection conversion ratio and selectivity, calculate the yield for obtaining epoxychloropropane.Above-mentioned reality is repeated several times
It tests, the results are shown in Table 1.
Application examples 13
From table 1 it can be seen that the catalyst effect produced under the conditions of embodiment 1 is best, therefore the catalysis in Example 1
Agent carries out recycling effect disquisition.Reaction condition is identical as application examples 12, is added 454 in the glass reaction kettle of 5 L
30% hydrogen peroxide of g, 53.4 g of catalyst produced in 306 g chloropropenes and embodiment 1.Mixed liquor is reacted at 55 DEG C
6 h, cooling, the epoxychloropropane of lower layer is cooled to 10 DEG C, a large amount of white catalyst solid is precipitated by liquid separation, is filtered, and is used
Dehydrated alcohol washing, dry, the recovery per pass of catalyst is 93%.Cyclic test is carried out with the catalyst of recycling, passes through gas phase
Chromatography detects conversion ratio and selectivity, calculates the yield for obtaining epoxychloropropane, the results are shown in Table 2.
The catalyst chloropropene produced under 1. different condition of table produces the effect of epoxychloropropane
The recycling effect of 2. catalyst of table
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.The embodiment of the present invention
Detailed description be not intended to limit the range of claimed invention, but be merely representative of selected embodiment of the invention.
Claims (7)
1. a kind of preparation method of the phosphorus heteropoly tungstic acid salt catalyst for synthesizing epoxy chloropropane, which is characterized in that it includes
Following steps:
K-type phosphotungstic acid is dissolved in oxidation reaction in 30% hydrogen peroxide and obtains peroxide phosphotungstic acid aqueous solution, then by peroxide phosphorus tungsten
Aqueous acid is added drop-wise in the ethanol solution of dimethyldioctadecylammonium ammonium chloride, and 2 h are stirred to react under the conditions of 40 DEG C；Reaction knot
White powder is filtered to obtain after beam, by washing, dehydrated alcohol is washed, and is dried in vacuo, and dimethyldioctadecylammonium base peroxide phosphorus tungsten is obtained
Acid catalyst.
2. a kind of preparation method of the phosphorus heteropoly tungstic acid salt catalyst for synthesizing epoxy chloropropane as described in claim 1,
It is characterized by: the molar ratio of K-type phosphotungstic acid and hydrogen peroxide is 1:20~1:40.
3. a kind of preparation method of the phosphorus heteropoly tungstic acid salt catalyst for synthesizing epoxy chloropropane as described in claim 1,
It is characterized by: K-type phosphotungstic acid is dissolved in hydrogen peroxide, the two is protected from light at room temperature is stirred to react 2 h.
4. a kind of preparation method of the phosphorus heteropoly tungstic acid salt catalyst for synthesizing epoxy chloropropane as described in claim 1,
It is characterized by: the molar ratio of K-type phosphotungstic acid and dimethyldioctadecylammonium ammonium chloride is 1:3~1:4.
5. a kind of preparation method of the phosphorus heteropoly tungstic acid salt catalyst for synthesizing epoxy chloropropane as described in claim 1,
It is characterized by: dimethyldioctadecylammonium ammonium chloride is added in appropriate dehydrated alcohol, stirring and dissolving at 40 DEG C.
6. a kind of preparation method of the phosphorus heteropoly tungstic acid salt catalyst for synthesizing epoxy chloropropane as described in claim 1,
It is characterized by: the peroxide phosphotungstic acid aqueous solution that reaction obtains is slowly added into dimethyldioctadecylammonium ammonium chloride dropwise
In ethanol solution, it is vigorously stirred 2 h of reaction.
7. a kind of preparation method of the phosphorus heteropoly tungstic acid salt catalyst for synthesizing epoxy chloropropane as described in claim 1,
It is characterized by: cooling down after reaction, it is filtered under diminished pressure, obtains white powder, is washed with a large amount of distillation, then with a small amount of second
Alcohol is washed, last 30 DEG C of vacuum drying.
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| CN114591268A (en) * | 2022-04-01 | 2022-06-07 | 福州大学 | Method for synthesizing alpha-epoxy pinane by epoxidation of alpha-pinene |
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| CN116375667A (en) * | 2023-06-04 | 2023-07-04 | 北京世纪迈劲生物科技有限公司 | Epoxidation method of 3-cyclohexene-1-carboxylic acid-3-cyclohexene-1-ylmethyl ester |
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