CN106967013A - A kind of Sc CO2The method that β methyl epichlorohydrins are prepared in system - Google Patents
A kind of Sc CO2The method that β methyl epichlorohydrins are prepared in system Download PDFInfo
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- CN106967013A CN106967013A CN201710125110.4A CN201710125110A CN106967013A CN 106967013 A CN106967013 A CN 106967013A CN 201710125110 A CN201710125110 A CN 201710125110A CN 106967013 A CN106967013 A CN 106967013A
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- epoxy chloropropane
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention discloses a kind of Sc CO2The method that β methyl epichlorohydrins are prepared in system, reaction raw materials hydrogen peroxide in advance with through refrigeration, pressurization, preheating supercritical carbon dioxide solvent（SC‑CO2）Mixed in blender to appropriate input concentration, then with after buffer sal volatile regulation pH value, add metering not only as raw material but also simultaneously as cosolvent β methylallyl chlorides, epoxidation reaction is carried out into the calandria type fixed bed layer reactor filled with Ti MWW titanium-silicon molecular sieve catalysts, product produces β methyl epichlorohydrins after rectifying.Whole building-up process of the invention, easy to operate, cost is low; yield is high, saves and free from environmental pollution, and carried out effective utilization to greenhouse gases carbon dioxide; there is very great meaning to environmental protection, be a kind of typical " atom economy " synthesis route.
Description
Technical field
The present invention relates to organic chemical synthesis technical field, more particularly, to a kind of Sc-CO2Beta-methyl ring is prepared in system
The method of oxygen chloropropane.
Background technology
β methyl epoxy chloropropane, also known as 2- methyl -3- epichlorohydrins, methyl epichlorohydrin, 2- chloromethyl -2- first
Hexadecyl ethylene oxide.English name β-methyl epichlorohydrin, abbreviation β-MECH, MECH.Molecular formula C4H7Cl, molecule
Measure 106.55, CAS 598-09-4, No. EINECS：209-916-7.It is a kind of colourless transparent oil liquid under normal temperature and pressure.
β methyl epoxy chloropropane (MECH) contains active epoxy bond and carbon chlorine key, with stronger reactivity, and
Epoxychloropropane is the same, mainly for the production of epoxy resin.There is following advantage compared with epichlorohydrin resin in performance:
(1) good mechanical performance, and with excellent ultra-violet resistance and against weather；(2) have preferably encompassing with other resins
Property；(3) small toxicity, and with good dissolubility, intersolubility and low viscosity；(4) there is excellent electrical insulating property, dielectric is strong
Degree is high, and resistance to electric arc ability is strong, available for preparing high-performance electric insulating materials.
Methyl epoxy resin is doped in PET (polyethylene terephthalate), PET molecule is significantly improved
Amount, and then improve its intensity and hardness.
With bisphenol-A and MECH etc., a series of adhesive has been synthesized, generation during metal smelt can be reclaimed well
Metal and its oxide powder, realize the secondary utilization of resource.
The external preparation about β methyl epoxy chloropropane has following several method through retrieval：
1st, chlorohydrination
This method is that big Japanese ink chemical company is studied successfully in nineteen sixty-eight earliest.Beta-methyl epoxy chloropropionate is synthesized as one kind
The indirect method of alkane, its course of reaction is mainly made up of 2 steps.First, Beta-methyl chloropropene hypochlorination is into 1,3=dichloro isopropyl
Alcohol, then adds alkali such as Ca (OH)2Synthesize β methyl epoxy chloropropane.The outstanding problem that this method is present is, generates β-first
Produced while base epoxychloropropane and largely contain CaCl2Waste water, the environmental problem thus triggered greatly threatens this method
Existence and further development.
2 direct synthesis techniques
2. 1 using oxygen as oxidant
Oxygen is a kind of oxidant cheap and easy to get, the use of oxygen is that oxidant can substantially reduce production cost.With chlorohydrination phase
Than Beta-methyl chloro propylene epoxidation being synthesized into β methyl epoxy chloropropane directly by oxidant of oxygen, with simplified reaction stream
Journey, by-product is not largely containing CaCl2Waste water the advantages of.But from the point of view of research level, the research of this respect is also in exploration rank
, there are many problems in section.
Sh. K. Kyazimov etc. are using silver nitrate as catalyst, using dimethyl phthalate as solvent, 150-160
Under the conditions of DEG C, Beta-methyl chloro propylene epoxidation is successfully realized in the reactor of designed, designed and synthesizes corresponding Beta-methyl epoxy chlorine
Propane.As a result show that reaction effect is poor, flow is complex.In addition, its used silver nitrate catalyst not only hold high by price
It is expensive, and reclaim more difficult.
Nissan Chem Ind company Li9H9 [ Li4V 12 B32O84]15H20 is catalyst, oxygen or air and β-
Methylallyl chloride reacts, and has successfully synthesized β methyl epoxy chloropropane.The reaction system of this method is complex, except reaction
Outside thing Beta-methyl chloropropene and catalyst, isobutyl aldoxime, acetonitrile and methanol are also added into.In terms of reaction effect, Beta-methyl chlorine third
The conversion ratio of alkene is up to 96.7%, and selectivity of product is up to 84.4%.At present, the technology is still in conceptual phase, further phase
Report is closed to have not been reported.
2.2 using peroxide as oxidant
2.2.1 alkyl peroxide
The Ti-Si catalyst that Mitsui Toatsu Chemicals companies are voluntarily synthesized using it, under conditions of more gently
（0~250 DEG C）, with alkyl peroxide (such as ethylbenzene hydroperoxide, dicumyl peroxide, tert-butyl peroxide and cyclohexyl mistake
Oxide etc.) realize the course of reaction that β methyl epoxy chloropropane is synthesized by Beta-methyl chloro propylene epoxidation for oxidant.From
From the point of view of document report, this method can reach higher yield and conversion ratio.As a result show, Beta-methyl chloropropene synthesis Beta-methyl
The conversion ratio and product yield of epoxychloropropane are respectively 94% and 80%.But, this current technology is still in laboratory research
Stage, therefore the industrial prospect of the method need further technical economic analysis.
2.2.2 hydrogen peroxide
The exploitations such as Carlo Venturello a kind of new homogeneous catalyst [（C8H17）3NCH3]3 { P04 [W (O)
(O2)2]4, epoxidation reaction can be carried out with efficient catalytic alkene and hydrogen peroxide and generate corresponding epoxides, Beta-methyl chlorine third
The selectivity of alkene is up to 85%.But difficulty is separated because this kind of catalyst is expensive, and after reaction, therefore there is not yet is urged using this
The report of the further research of agent synthesis β methyl epoxy chloropropane.
Tamayuki Kitano etc. introduce ultrasound in the reaction medium that TS-1 is catalyzed Beta-methyl chloro propylene epoxidation process
Reinforcement technique.As a result show, in the case of other conditions identical, without using ultrasound-enhanced means, hydrogen peroxide turns after reaction 4h
Rate and selectivity of product are respectively 97% and 65.7%, and under ultrasound-enhanced, hydrogen peroxide conversion is just reachable after reaction 2h
97%, selectivity of product can be then improved to 81%.They think, can be with the acidic site on specific ions screen TS-1 catalyst
The β methyl epoxy chloropropane for suppressing reaction generation is hydrolyzed into glycol, so as to improve the selectivity of reaction.It is the most noticeable
It is that they propose and successfully realized
TS-1 catalysis Beta-methyls chloropropene synthesizes the course of reaction of β methyl epoxy chloropropane under condition of no solvent, and points out not
The research come can extend to without using the field that β methyl epoxy chloropropane is synthesized under solvent condition.
Publication number：101205220, the Chinese patent in publication date on June 25th, 2008 discloses a kind of methylallyl chloride and used
Reaction control phase transfer catalyst catalysis epoxidation produces the new method of methyl epichlorohydrin.This kind of catalyst is not dissolved in itself
In reaction medium, but in the presence of hydrogen peroxide, the active specy dissolved in reaction medium, and then and methyl can be formed
Chloropropene is acted on, and it is carried out epoxidation reaction with high selectivity, and methylallyl chloride is to the conversion ratio of hydrogen peroxide up to 96%, first
Base epoxychloropropane is 95% to the selectivity of methylallyl chloride；And when hydrogen peroxide is depleted, catalyst is i.e. from reactant
Separated out in system, by simply separating, catalyst just can be with recycling use.The separation of this kind of catalyst and heterogeneous catalyst
It is similar, and the characteristics of then embody homogeneous catalyst completely during the course of the reaction.
But the drawbacks of preparation method one is that this phase transfer catalyst is expensive, economy is to restrict the preparation method
Key factor.
The content of the invention
The present invention is asked to solve the above-mentioned technology present in the β methyl epoxy chloropropane preparation method of prior art
Topic is there is provided a kind of advanced technology, and cost is low, and yield is high, safe and environment-friendly Sc-CO2Beta-methyl epoxy chloropropionate is prepared in system
The method of alkane.
To achieve these goals, the present invention uses following technical scheme：
A kind of Sc-CO2The method that β methyl epoxy chloropropane is prepared in system, comprises the following steps：
（1）By hydrogen peroxide in advance with through refrigeration, pressurization after supercritical carbon dioxide（Sc-CO2）Mixed in blender to institute
Adjusted after the input concentration needed with buffer solution to pH to 6 ~ 7, add Beta-methyl chloropropene and be mixed with forming Sc-CO2Mixing
Fluid, after the preheated device preheating of fluid-mixing, is delivered to filled with the calandria type fixed bed of Ti-MWW titanium-silicon molecular sieve catalysts
Epoxidation reactor carries out epoxidation reaction, obtains the thick solution of β methyl epoxy chloropropane.Sc-CO in the present invention2With excellent
Beta-methyl chloropropene, is substantially dissolved in wherein, is diffused rapidly to reaction substrate by different dissolving and mass-transfer performance as solvent
Ti-MWW active sites are reacted, and eliminate surface resistance to mass tranfer, in addition, H2O2Energy and CO2React generation percarbonic acid root from
Son, carbanion can promote the progress that Beta-methyl chloro propylene epoxidation reacts；Beta-methyl chloropropene is not only as raw material but also same
Shi Zuowei cosolvent；Weakly alkaline ammonium carbonate can not only neutralize one to the further optimization of Beta-methyl chloro propylene epoxidation reaction
Partially acidic reduces side reaction, moreover it is possible to H202With reference to playing a part of buffer, during the course of the reaction gradually by H202Release
Into reaction system, H is reduced202Decomposition, improve H202Utilization rate.And effectively inhibit ring-opening reaction pair
The formation of product.
（2）The thick solution of β methyl epoxy chloropropane is delivered to pre-separation tower and carries out two-phase laminated flow, the organic phase after separation
Rectifying is carried out into rectifying column, β methyl epoxy chloropropane is obtained.Sc-CO2Organic matter formation organic phase in aqueous phase can be extracted
And it is separated from the water, organic phase enters rectifying column, successively by the complete Beta-methyl chloropropene of unreacted, a small amount of Beta-methyl chlorine third
Alkene hydrolysate methallyl alcohol and β methyl epoxy chloropropane open-loop products dibastic alcohol compound are separated, final real
Now to the cleaning of product β methyl epoxy chloropropane, quickly separation.
Preferably, step（1）In, Beta-methyl chloropropene and H2O2Mol ratio control be（1.0~3.5）：1, preheater
Preheating temperature is 32 ~ 35 DEG C.
Preferably, step（1）In, the mass space velocity of charging is 10 ~ 30/h-1, the reaction temperature of epoxidation reaction for 45 ~
60 DEG C, reaction pressure is 7.6 ~ 16MPa.Mass space velocity=material quality flow（kg.h-1）/ catalyst quality（kg）.
Preferably, step（2）In, the Operating parameters of pre-separation tower are：7.6 ~ 16MPa of pressure；Temperature is 32 ~ 85
℃。
Preferably, step（2）In, the Operating parameters of rectifying tower are：35 ~ 65 DEG C of tower top temperature, column bottom temperature
55 ~ 120 DEG C, pressure -0.05 ~ -0.0999MPa.
Therefore, the present invention has the advantages that：With Sc-CO2Mixed for solvent, and hydrogen peroxide, buffered dose of carbonic acid
After ammonium regulation pH value, add not only as raw material but also simultaneously as the Beta-methyl chloropropene of cosolvent, into filled with Ti-MWW
The calandria type fixed bed layer reactor of titanium-silicon molecular sieve catalyst carries out epoxidation reaction, and product produces Beta-methyl ring after rectifying
Oxygen chloropropane, whole building-up process, easy to operate, cost is low, and yield is high, saves and free from environmental pollution, and to greenhouse effects gas
Body carbon dioxide has carried out effective utilization, has very great meaning to environmental protection, is a kind of typical " atom economy "
Synthesis route.
Embodiment
Below by embodiment, the present invention will be further described.
Embodiment 1
（1）By hydrogen peroxide in advance with through refrigeration, pressurization after supercritical carbon dioxide（Sc-CO2）Mixed in blender to institute
Adjusted after the input concentration needed with buffer solution to pH to 6 ~ 7, add Beta-methyl chloropropene and be mixed with forming Sc-CO2Mixing
Fluid, the preheated device of fluid-mixing obtains Sc-CO after being preheated to 32 DEG C2Fluid-mixing, after being adjusted to 6 with sal volatile, conveying
To filled with Ti-MWW titanium-silicon molecular sieve catalysts calandria type fixed bed epoxidation reactor carry out epoxidation reaction, obtain β-
The thick solution of methyl epichlorohydrin, wherein, Beta-methyl chloropropene and H2O2Mol ratio control be 1.0：1, the mass space velocity of charging
For 10/h-1, the reaction temperature of epoxidation reaction is 45 DEG C, and reaction pressure is 7.6MPa；
（2）The thick solution of β methyl epoxy chloropropane is delivered to pre-separation tower and carries out two-phase laminated flow, the organic phase after separation enters
Rectifying column carries out rectifying, obtains β methyl epoxy chloropropane, the Operating parameters of wherein pre-separation tower are：Pressure 7.6MPa；
Temperature is 32 DEG C, and the Operating parameters of rectifying tower are：35 DEG C of tower top temperature, 55 DEG C of column bottom temperature, pressure -0.05MPa.
Embodiment 2
（1）By hydrogen peroxide in advance with through refrigeration, pressurization after supercritical carbon dioxide（Sc-CO2）Mixed in blender to institute
Adjusted after the input concentration needed with buffer solution to pH to 6 ~ 7, add Beta-methyl chloropropene and be mixed with forming Sc-CO2Mixing
Fluid, the preheated device of fluid-mixing obtains Sc-CO after being preheated to 35 DEG C2Fluid-mixing, after being adjusted to 7 with sal volatile, conveying
To filled with Ti-MWW titanium-silicon molecular sieve catalysts calandria type fixed bed epoxidation reactor carry out epoxidation reaction, obtain β-
The thick solution of methyl epichlorohydrin, wherein, Beta-methyl chloropropene and H2O2Mol ratio control be 3.5：1, the mass space velocity of charging
For 30/h-1, the reaction temperature of epoxidation reaction is 60 DEG C, and reaction pressure is 16MPa；
（2）The thick solution of β methyl epoxy chloropropane is delivered to pre-separation tower and carries out two-phase laminated flow, the organic phase after separation enters
Rectifying column carries out rectifying, obtains β methyl epoxy chloropropane, the Operating parameters of wherein pre-separation tower are：Pressure 16MPa；Temperature
Spend for 85 DEG C, the Operating parameters of rectifying tower are：65 DEG C of tower top temperature, 120 DEG C of column bottom temperature, pressure -0.0999MPa.
Embodiment 3
（1）By hydrogen peroxide in advance with through refrigeration, pressurization after supercritical carbon dioxide（Sc-CO2）Mixed in blender to institute
Adjusted after the input concentration needed with buffer solution to pH to 6 ~ 7, add Beta-methyl chloropropene and be mixed with forming Sc-CO2Mixing
Fluid, the preheated device of fluid-mixing obtains Sc-CO after being preheated to 33 DEG C2Fluid-mixing, it is defeated after being adjusted to 6.5 with sal volatile
Deliver to the calandria type fixed bed epoxidation reactor filled with Ti-MWW titanium-silicon molecular sieve catalysts and carry out epoxidation reaction, obtain
The thick solution of β methyl epoxy chloropropane, wherein, Beta-methyl chloropropene and H2O2Mol ratio control be 2：1, the mass space velocity of charging
For 20/h-1, the reaction temperature of epoxidation reaction is 50 DEG C, and reaction pressure is 8MPa；
（2）The thick solution of β methyl epoxy chloropropane is delivered to pre-separation tower and carries out two-phase laminated flow, the organic phase after separation enters
Rectifying column carries out rectifying, obtains β methyl epoxy chloropropane, the Operating parameters of wherein pre-separation tower are：Pressure 12MPa；Temperature
Spend for 60 DEG C, the Operating parameters of rectifying tower are：40 DEG C of tower top temperature, 70 DEG C of column bottom temperature, pressure -0.05 ~ -
0.0999MPa。
Whole building-up process of the invention, easy to operate, cost is low, and yield is high, and the yield of β methyl epoxy chloropropane is reachable
92.3 ~ 99.36%, selectivity is 93.5 ~ 99.80%, is saved and free from environmental pollution, and greenhouse gases carbon dioxide is carried out
Effective utilization, has very great meaning to environmental protection, is a kind of typical " atom economy " synthesis route.
Embodiment described above is a kind of preferably scheme of the present invention, not makees any formal to the present invention
Limitation, also has other variants and remodeling on the premise of without departing from the technical scheme described in claim.
Claims (5)
1. a kind of Sc-CO2The method that β methyl epoxy chloropropane is prepared in system, it is characterised in that comprise the following steps：
（1）By hydrogen peroxide in advance with through refrigeration, pressurization after supercritical carbon dioxide（Sc-CO2）Mixed in blender to required
Input concentration after adjusted with buffer solution to pH to 6 ~ 7, add Beta-methyl chloropropene and be mixed with forming Sc-CO2Mixed flow
Body, after the preheated device preheating of fluid-mixing, is delivered to the calandria type fixed bed ring filled with Ti-MWW titanium-silicon molecular sieve catalysts
Oxidation reactor carries out epoxidation reaction, obtains the thick solution of β methyl epoxy chloropropane；
（2）The thick solution of β methyl epoxy chloropropane is delivered to pre-separation tower and carries out two-phase laminated flow, the organic phase after separation enters
Rectifying column carries out rectifying, obtains β methyl epoxy chloropropane.
2. a kind of Sc-CO according to claim 12The method that β methyl epoxy chloropropane is prepared in system, its feature exists
In step（1）In, Beta-methyl chloropropene and H2O2Mol ratio control be（1.0~3.5）：1, preheater preheating temperature is 32 ~ 35
℃。
3. a kind of Sc-CO according to claim 1 or 22The method that β methyl epoxy chloropropane is prepared in system, its feature
It is, step（1）In, the mass space velocity of charging is 10 ~ 30/h-1, the reaction temperature of epoxidation reaction is 45 ~ 60 DEG C, reaction pressure
Power is 7.6 ~ 16MPa.
4. a kind of Sc-CO according to claim 12The method that β methyl epoxy chloropropane is prepared in system, its feature exists
In step（2）In, the Operating parameters of pre-separation tower are：7.6 ~ 16MPa of pressure；Temperature is 32 ~ 85 DEG C.
5. a kind of Sc-CO according to claim 12The method that β methyl epoxy chloropropane is prepared in system, its feature exists
In step（2）In, the Operating parameters of rectifying tower are：35 ~ 65 DEG C of tower top temperature, 55 ~ 120 DEG C of column bottom temperature, pressure-
0.05~-0.0999MPa。
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| CN201710125110.4A CN106967013B (en) | 2017-03-03 | 2017-03-03 | A kind of Sc-CO2The method of β methyl epoxy chloropropane is prepared in system |
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| CN201710125110.4A CN106967013B (en) | 2017-03-03 | 2017-03-03 | A kind of Sc-CO2The method of β methyl epoxy chloropropane is prepared in system |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116143727A (en) * | 2023-02-09 | 2023-05-23 | 浙江皇马科技股份有限公司 | Refining method of methyl epoxy chloropropane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456849A (en) * | 2008-12-30 | 2009-06-17 | 清华大学 | Method and apparatus for preparing epoxypropane by catalyzing propone epoxidation at supercritical condition |
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2017
- 2017-03-03 CN CN201710125110.4A patent/CN106967013B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456849A (en) * | 2008-12-30 | 2009-06-17 | 清华大学 | Method and apparatus for preparing epoxypropane by catalyzing propone epoxidation at supercritical condition |
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| TOMOYUKI KITANO，等: "The Epoxidation of Allychlorides with Hydrogen Peroxide over TS-1", 《SCIENCE AND TECHNOLOGY IN CATALYSIS》 * |
| 上海市经济团体联合会，等: "《节能减排新途径与新技术》", 31 May 2010, 华东理工大学出版社 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116143727A (en) * | 2023-02-09 | 2023-05-23 | 浙江皇马科技股份有限公司 | Refining method of methyl epoxy chloropropane |
| CN116143727B (en) * | 2023-02-09 | 2024-05-07 | 浙江皇马科技股份有限公司 | Refining method of methyl epoxy chloropropane |
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