CN104098531A - Synthetic method for 1,2-epoxybutane - Google Patents
Synthetic method for 1,2-epoxybutane Download PDFInfo
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- CN104098531A CN104098531A CN201410361395.8A CN201410361395A CN104098531A CN 104098531 A CN104098531 A CN 104098531A CN 201410361395 A CN201410361395 A CN 201410361395A CN 104098531 A CN104098531 A CN 104098531A
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- oxide ring
- butylene oxide
- synthetic method
- butylene
- hydrogen peroxide
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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
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a synthetic method for 1,2-epoxybutane. The method mainly comprises the step that the 1,2-epoxybutane is prepared through an one-step oxidation method, wherein an oxidizing agent is hydrogen peroxide. The synthetic method is simple in technological process, high in reaction yield, relatively low in preparation cost, and environmentally friendly in the whole process.
Description
Technical field
The present invention relates to a kind of synthesis technique of organic chemical industry's intermediate, be specifically related to the synthetic novel process of a kind of 1,2-butylene oxide ring.
Background technology
1,2-butylene oxide ring (BO), claim again oxybutylene, it is a kind of important organic chemical industry's intermediate, purposes is very extensive, thinner, the reference material of stratographic analysis etc. mainly for the manufacture of intermediate and polymkeric substance, replacement acetone as pyroxylin(e)finish, also can be used as chlorine-containing compound oxidation inhibitor, produce corrosion inhibitor, tensio-active agent, the gasoline dope, 1 of vinyl chloride resin, 1,1-trichloroethane (CH
3-CCl
3) and the stablizer of other chlorinated solvent etc.
The production line of 1,2-butylene oxide ring has chlorohydrination, direct oxidation method and indirect oxidation method.Industrial 1, the main production method of 2-butylene oxide ring still adopts chlorohydrination technique so far, first makes 1-butylene chlorohydrination with hypochlorous acid, then obtains 1,2-butylene oxide ring through saponification.While adopting synthetic 1, the 2-butylene oxide ring of this technique, need to consume a large amount of Cl
2, equipment corrosion is serious, and produces containing CaCl in producing
2waste water, waste residue with organic chloride, caused very big pollution to environment, do not meet the requirement of Green Chemistry and cleaner production, and therefore, along with the raising day by day of environmental protection requirement, this technique certainly will will be eliminated.
In recent years, the method for 1-butylene Direct Epoxidation generation 1,2-butylene oxide ring under catalyst action is causing people's concern.Adopt Direct Epoxidation method to produce 1,2-butylene oxide ring and not only optimized Production Flow Chart, also reduced environmental pollution.At present, substantially adopting hydrogen peroxide is that oxygen source carries out epoxidation reaction, and the main deficiency of existence is that 1,2-butylene oxide ring selectivity is low, yield is low, can not continuous reaction.
Summary of the invention
The present invention, from optimization technological process, raising selectivity, raising reaction yield, serialization production equal angles, has proposed the synthetic novel process of a kind of 1,2-butylene oxide ring.
To achieve these goals, the present invention adopts following technical scheme:
A kind of 1, the synthetic method of 2-butylene oxide ring, the method comprises the following steps: the toluene that is 1:0.5~5:0.8~3 by mol ratio, tributyl phosphate, mass concentration are that the mixed solution of 30%~80% hydrogen peroxide obtains working fluid after dehydration, in working fluid, be filled with 1-butylene, be that under 50~100 DEG C, pressure 0.1~0.8Mpa and catalyzer exist, reaction generates 1 in temperature, 2-butylene oxide ring, wherein, 1-butylene and mass concentration are that 30%~80% hydrogen peroxide mol ratio is 2~5:1.The reaction times of the method is 2~8h.In preferred mixed solution, toluene, tributyl phosphate, mass concentration are that the mol ratio of 30%~80% hydrogen peroxide is 1:0.5~3:0.8~3.Preferred reaction pressure is 0.1~0.6Mpa, and preferable reaction temperature is 50~90 DEG C.
Described catalyzer is a kind of in silicotungstic heteropolyacid salt, phospho heteropoly tungstate, phosphato-molybdic heteropolyacid salt or their any mixture.Described mixture can be any two kinds of mixing in silicotungstic heteropolyacid salt, phospho heteropoly tungstate, phosphato-molybdic heteropolyacid salt.
Catalyst levels of the present invention is 1~3% with respect to the mass concentration of working fluid.
Described catalyzer is capable of circulation to be applied mechanically 2~10 times.
The present invention can use a kind of in fixed-bed reactor, fluidized-bed reactor, pipeline reactor or their combination.
Beneficial effect of the present invention compared with the prior art: the present invention adopts this one-step oxidation process synthetic 1,2-butylene oxide ring, the defects such as the equipment corrosion that chlorohydrination causes is serious, environmental pollution are overcome, whole process is simple, pollution-free, can be continuously produced, the selectivity of 1,2-butylene oxide ring can reach more than 99%, and 1,2-butylene oxide ring can reach more than 95% the productive rate of hydrogen peroxide, is suitable for large-scale industrial production.
Embodiment
By specific embodiment, the present invention is further expalined to explanation below:
Wherein, silicotungstic heteropolyacid salt (molecular formula SiO
2wO
324H
2o, Chemical Reagent Co., Ltd., Sinopharm Group), phospho heteropoly tungstate (molecular formula H
3pW
12o
40, Shenyang Chemical Reagent Co., Ltd., Sinopharm Group), phosphato-molybdic heteropolyacid salt (molecular formula H
3pMo
12o
40, Shenyang Chemical Reagent Co., Ltd., Sinopharm Group)
Embodiment 1:
The mixed solution of the toluene that is 1:0.5:0.8 by mol ratio, tributyl phosphate, 30% (mass concentration) hydrogen peroxide injects water trap and after decompression dehydration, obtains working fluid, in working fluid, be filled with 1-butylene, there is lower reaction 2h in temperature 50 C, pressure 0.1Mpa and catalyzer silicotungstic heteropolyacid salt, catalyzed oxidation 1-butylene generates 1,2-butylene oxide ring.Wherein, 1-butylene and 30% hydrogen peroxide mol ratio are 2:1, and the mass concentration of catalyzer is 1% (with respect to working fluid).Products therefrom is through stratographic analysis, and the selectivity of 1,2-butylene oxide ring is that 99.2%, 1,2-butylene oxide ring is 95.6% to the productive rate of hydrogen peroxide.
Embodiment 2:
The mixed solution of the toluene that is 1:1.5:2.6 by mol ratio, tributyl phosphate, 50% (mass concentration) hydrogen peroxide injects water trap and after decompression dehydration, obtains working fluid, in working fluid, be filled with 1-butylene, reaction 4h under temperature 70 C, pressure 0.3Mpa and catalyzer silicotungstic heteropolyacid salt and phosphorus heteropoly tungstic acid salt mixture (mass ratio 1:1) existence, catalyzed oxidation 1-butylene generates 1,2-butylene oxide ring.Wherein, 1-butylene and 50% hydrogen peroxide mol ratio are 4:1, and the mass concentration of catalyzer is 1.5% (with respect to working fluid).Products therefrom is through stratographic analysis, and the selectivity of 1,2-butylene oxide ring is that 99.5%, 1,2-butylene oxide ring is 96.3% to the productive rate of hydrogen peroxide.
Embodiment 3:
The mixed solution of the toluene that is 1:0.8:1.5 by mol ratio, tributyl phosphate, 50% (mass concentration) hydrogen peroxide injects water trap and after decompression dehydration, obtains working fluid, in working fluid, be filled with 1-butylene, under existing, 70 DEG C of certain temperatures, pressure 0.5Mpa and catalyzer phospho heteropoly tungstate react 5h, catalyzed oxidation 1-butylene generates 1,2-butylene oxide ring.Wherein, 1-butylene and 50% hydrogen peroxide mol ratio are 3:1, and the mass concentration of catalyzer is 2.0% (with respect to working fluid).Products therefrom is through stratographic analysis, and the selectivity of 1,2-butylene oxide ring is that 99.6%, 1,2-butylene oxide ring is 96.8% to the productive rate of hydrogen peroxide.
Embodiment 4:
The mixed solution of the toluene that is 1:3:3 by mol ratio, tributyl phosphate, 80% (mass concentration) hydrogen peroxide injects water trap and after decompression dehydration, obtains working fluid, in working fluid, be filled with 1-butylene, under existing, 90 DEG C of temperature, pressure 0.6Mpa and catalyzer react 7h, catalyzed oxidation 1-butylene generates 1,2-butylene oxide ring.Wherein, 1-butylene and 80% hydrogen peroxide mol ratio are 5:1, and catalyzer is phospho heteropoly tungstate and phosphato-molybdic heteropolyacid salt mixture (mass ratio is 1:1), and catalyst concn is 3.0% (with respect to working fluid).Products therefrom is through stratographic analysis, and the selectivity of 1,2-butylene oxide ring is that 99.3%, 1,2-butylene oxide ring is 95.8% to the productive rate of hydrogen peroxide.
Comparative example:
Utilize the technology of preparing of 2-butylene as synthetic 1, the 2-butylene oxide ring of raw material, its technical process is as follows:
Utilize this flow process to synthesize 1,2-butylene oxide ring, the transformation efficiency of 2-butylene in reaction process is more than 95%, but its selectivity only has 63%, and total recovery only has 60%.
Claims (8)
1. one kind 1, the synthetic method of 2-butylene oxide ring, is characterized in that the method comprises the following steps:
The toluene that is 1:0.5~5:0.8~3 by mol ratio, tributyl phosphate, mass concentration are that the mixed solution of 30%~80% hydrogen peroxide obtains working fluid after dehydration, in working fluid, be filled with 1-butylene, be that under 50~100 DEG C, pressure 0.1~0.8Mpa and catalyzer exist, reaction generates 1 in temperature, 2-butylene oxide ring, wherein, 1-butylene and mass concentration are that 30%~80% hydrogen peroxide mol ratio is 2~5:1.
2. according to claim 11, the synthetic method of 2-butylene oxide ring, the reaction times that it is characterized in that the method is 2~8h.
3. according to claim 11, the synthetic method of 2-butylene oxide ring, is characterized in that toluene, tributyl phosphate, mass concentration in described mixed solution are that the mol ratio of 30%~80% hydrogen peroxide is 1:0.5~3:0.8~3.
4. according to claim 11, the synthetic method of 2-butylene oxide ring, is characterized in that described reaction pressure is 0.1~0.6Mpa, and temperature of reaction is 50~90 DEG C.
5. according to claim 11, the synthetic method of 2-butylene oxide ring, is characterized in that described catalyzer is a kind of in silicotungstic heteropolyacid salt, phospho heteropoly tungstate, phosphato-molybdic heteropolyacid salt or their any mixture.
6. according to claim 51, the synthetic method of 2-butylene oxide ring, is characterized in that described mixture is any two kinds of mixing in silicotungstic heteropolyacid salt, phospho heteropoly tungstate, phosphato-molybdic heteropolyacid salt.
7. according to claim 11, the synthetic method of 2-butylene oxide ring, is characterized in that described catalyzer is 1~3% with respect to the mass concentration of working fluid.
8. according to claim 11, the synthetic method of 2-butylene oxide ring, is characterized in that described catalyst recirculation applies mechanically 2~10 times.
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Publication number | Priority date | Publication date | Assignee | Title |
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CN113292518A (en) * | 2021-06-22 | 2021-08-24 | 中山大学 | Method for preparing epoxybutane by organic micromolecule green and efficient catalysis of butylene |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101045716A (en) * | 2006-03-27 | 2007-10-03 | 中国石油化工股份有限公司 | Production method of epoxy propane |
CN101045717A (en) * | 2006-03-27 | 2007-10-03 | 中国石油化工股份有限公司 | Method of directly catalytic epoxidation |
CN101085763A (en) * | 2007-05-11 | 2007-12-12 | 湖南长岭石化科技开发有限公司 | Method for synthesizing 1,2-epoxy butane |
CN101613329A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of preparation method of propylene oxide |
CN103880783A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method for preparing epoxypropane by catalyzing propylene epoxidation with phase-transfer catalyst under reaction control |
CN103880782A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method for preparing epoxy propane |
CN103880779A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method utilizing quaternary ammonium heteropolyate to catalyze alkene epoxidation |
CN103880780A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Epoxidation method for preparing epoxy propane from liquid propylene |
-
2014
- 2014-07-25 CN CN201410361395.8A patent/CN104098531B/en not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101045716A (en) * | 2006-03-27 | 2007-10-03 | 中国石油化工股份有限公司 | Production method of epoxy propane |
CN101045717A (en) * | 2006-03-27 | 2007-10-03 | 中国石油化工股份有限公司 | Method of directly catalytic epoxidation |
CN101085763A (en) * | 2007-05-11 | 2007-12-12 | 湖南长岭石化科技开发有限公司 | Method for synthesizing 1,2-epoxy butane |
CN101613329A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of preparation method of propylene oxide |
CN103880783A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method for preparing epoxypropane by catalyzing propylene epoxidation with phase-transfer catalyst under reaction control |
CN103880782A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method for preparing epoxy propane |
CN103880779A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method utilizing quaternary ammonium heteropolyate to catalyze alkene epoxidation |
CN103880780A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Epoxidation method for preparing epoxy propane from liquid propylene |
Non-Patent Citations (3)
Title |
---|
KEIGO KAMATA等: "Efficient, regioselective epoxidation of dienes with hydrogen peroxide catalyzed by [γ -SiW10O34(H2O)2]4−", 《JOURNAL OF CATALYSIS》 * |
KEIGO KAMATA等: "Efficient, regioselective epoxidation of dienes with hydrogen peroxide catalyzed by [γ -SiW10O34(H2O)2]4−", 《JOURNAL OF CATALYSIS》, vol. 224, 31 December 2004 (2004-12-31), pages 224 - 228, XP 004504133, DOI: doi:10.1016/j.jcat.2004.02.027 * |
李军等: "反应控制相转移催化研究的进展", 《催化学报》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113292518A (en) * | 2021-06-22 | 2021-08-24 | 中山大学 | Method for preparing epoxybutane by organic micromolecule green and efficient catalysis of butylene |
CN113292518B (en) * | 2021-06-22 | 2022-05-31 | 中山大学 | Method for preparing epoxybutane by organic micromolecule green and efficient catalysis of butylene |
WO2022267081A1 (en) * | 2021-06-22 | 2022-12-29 | 中山大学 | Green and efficient method for catalyzing butene to prepare epoxybutane with organic small molecules |
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