CN103159703B - Method of continuously producing epichlorohydrin by directly epoxidizing chloropropene - Google Patents
Method of continuously producing epichlorohydrin by directly epoxidizing chloropropene Download PDFInfo
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Abstract
The invention discloses a method of continuously producing epichlorohydrin by directly epoxidizing chloropropene. The method of continuously producing epichlorohydrin by directly epoxidizing chloropropene includes: respectively transporting chloropropene, hydrogen peroxide, catalyst slurry or/and solvent to a reactor through a metering pump, the reactor is a single reactor or multistage reactors which are connected in series, reaction pressure is 0.1 to 1.0 MPa, and reaction liquid is in a homogeneous phrase state or a non-homogeneous phrase state. A filter is arranged at the upper end of a discharge port in the reactor to extract liquor with products, materials which are arranged at the lower end of the filter, are not filtered, contain catalyst and are not completely reacted is transported to the reactor through the metering pump which is arranged at the lower end of the reactor, the catalyst is free from recycling the catalyst in the continuous production process, and gaseous phrase portion conducts condensation reflux through a condenser which is arranged at the top of the reactor. The method of continuously producing epichlorohydrin by directly epoxidizing chloropropene has the advantages of being stable in reaction temperature and simple in process flow, the catalyst is free from being separated, beaten and configured again after reaction, the hydrogen peroxide is high in effective utilization and epichlorohydrin is high in yield, and method of continuously producing epichlorohydrin by directly epoxidizing chloropropene can be used in industry production.
Description
Technical field
What the present invention relates to is production unit and the production method of Chemicals epoxy chloropropane.Specifically, the present invention is a kind of take hydrogen peroxide as oxygenant, and the heteropolyacid salt that phase transition characteristic is controlled in reaction is catalyzer, directly the method for catalysis epoxidation propenyl chloride continuous production epoxy chloropropane.
Technical background
Epoxy chloropropane (Epichlorohydrin, ECH) be a kind of important basic chemical industry raw material, mainly for the production of multiple products such as epoxy resin, chlorohydrin rubber, glycerine and tensio-active agent, medicine, agricultural chemicals, coating, ion exchange resin, softening agent.Industrial process mainly contains chlorohydrination and allyl acetate-allyl alcohol method, chlorohydrination main raw material is propylene, chlorine and lime, and principal reaction technique is obtained by propylene high-temperature chlorination that propenyl chloride, propenyl chloride hypochlorination obtain dichlorohydrine, dichlorohydrine saponification obtains epoxy chloropropane three steps and forms.Chlorohydrination process characteristic: the feature with production maximization, serialization and automatization, and there is technical maturity, stable operation, but exist low conversion rate, by product is many, unit consumption is high, equipment is perishable, produce and to contain in a large number the shortcomings such as calcium chloride and organochlorine waste water.The main raw material of allyl acetate-allyl alcohol method is propylene, oxygen and acetic acid, principal reaction technique by propylene gas phase Catalytic Oxygen acetic acid acetic acid allyl processed vinegar, hydrolysis vinyl carbinol processed, form with chlorine addition synthesizing dichloropropanol and saponification dehydrochlorination four steps.Although allyl acetate-allyl alcohol method technique reaction conditions relaxes, by product is few, and chlorine and lime raw material consumption reduce by half, and have the shortcomings such as technique is tediously long, facility investment is high, the three wastes are many.In order effectively to solve the problems such as propenyl chloride method and allyl acetate-allyl alcohol method are produced exist seriously polluted, equipment is perishable, the direct oxidation of exploitation propenyl chloride is prepared epoxy chloropropane process for cleanly preparing and is arisen at the historic moment.The technique that epoxy chloropropane is prepared in current propenyl chloride direct oxidation is mainly and adopts HTS or Suanphosphotungstate as catalyzer, and hydrogen peroxide is that oxygenant reacts.
1988, people's reported first such as Carlo Venturello heteropoly acid catalysis chloro propylene epoxidation reaction, [the R of heteropolyacid in reaction process
4n
+]
3{ PO
4[WO (O
2)
2]
4}
3-for catalytic active species, aqueous hydrogen peroxide solution is oxygenant, and benzene is solvent, and after reacting 2.5 hours, the productive rate of epoxy chloropropane is 85%.CN1298876 discloses a kind of method of preparing epoxy chloropropane by catalytic epoxidation of chloropropene by molecular oxygen, take molecular oxygen as oxygenant, transition metal heteropolyacid salt is catalyzer, and the relative traditional technology of wastewater flow rate of generation significantly reduces, and catalyzer is recyclable.CN1900071 discloses the method for hydrogen peroxide direct oxidation propenyl chloride epoxy chloropropane processed.Although the disclosed reaction control phase transfer catalyst phosphorus heteropoly tungstic acid catalyzer of document has the activity of good catalysis hydrogen peroxide direct oxidation propenyl chloride epoxy chloropropane processed, solid but due to the own solid-liquid of catalyzer in its reaction process-phase transition feature, popular response technique is difficult to realize its large-scale continuous production.
EP065473A1 discloses a kind of trickle-bed reactor for chloro propylene epoxidation and generating process thereof, large granular catalyst divides four sections to be filled in trickle-bed reactor, intersegmental angry pipe and the hydrops plate of being provided with, first three section of bed is main reaction section, every section is provided with condenser and carries out heat exchange, this structure of reactor is complicated, working pressure is high, relies on systemic circulation Material control temperature, and granules of catalyst is too large, increase diffusional resistance, reduced the effective rate of utilization of catalyzer.
US4833260 discloses a kind of method that propenyl chloride Direct Epoxidation is prepared epoxy chloropropane, take HTS as catalyzer, hydrogen peroxide is oxygenant, propenyl chloride Direct Catalytic Oxidation is optionally produced epoxy chloropropane, the method has solved the problem that traditional technology a large amount of waste water causes environmental pollution, but because catalyst Ti-si molecular sieves need have higher catalytic activity in alcohols isopolarity solvent kind, the introducing of a large amount of polar solvents causes epoxy chloropropane generation part hydrolysis to generate ethers product, and the selectivity of product is low.The patents such as US4824976, US5675026, CN1319099, CN1219536A disclose to adopt and have added the organic or homopolar compound of alkalescence to improve catalyzer, thereby have improved the selectivity of epoxy chloropropane.
CN1769277A discloses a kind of epichlorohydrin production process, after being configured, liquid phase propenyl chloride and titanium-silicon molecular sieve catalyst join rotating bed with helix channel or rotating packed bed supergravity reactor, add continuously liquid phase or gas phase propenyl chloride and hydrogen peroxide, propenyl chloride and hydrogen peroxide directly carry out epoxidation reaction under the effect of catalyzer simultaneously.A small amount of gas of unreacted propenyl chloride and production returns to material-compound tank through condensation to be continued to use, in reactor, slurries flow into material-compound tank, after partial material pressurization, circulation enters reactor, partial material is sent separator, the epoxy chloropropane that goes out after separation is sent to refiningly, returns to material-compound tank continue to use containing the slurry of catalyzer.The method is not owing to being used solvent, and catalyzer is bad dispersibility in reaction process, and the activity of catalyzer and life-span can affect adversely, and catalyst separating adopts spinning liquid isolation technique in addition, operating process very complicated, is unfavorable for industrial production.
CN101172970A discloses a kind of method of producing epoxy chloropropane, take HTS as catalyzer, take hydrogen peroxide as oxygenant, take acetonitrile as solvent, take fixed bed as reactor, and catalyzed oxidation propenyl chloride is produced epoxy chloropropane.But must make reaction solution be homogeneous phase, therefore need to use a large amount of solvents to increase separating energy consumption, in catalyst reaction process in fixed-bed reactor, duct is easily stopped up in addition, easily cause productive rate low, in reaction process, heat release concentrates on beds, easily causes that by-product in production process increases, selectivity declines.
CN1275952C discloses a kind of production method of epoxy chloropropane, propenyl chloride, hydrogen peroxide, solvent and titanium-silicon molecular sieve catalyst fine particle are put into reactor and are reacted, solvent and unreacted propenyl chloride directly turn back to reactor through fractionator, slurries in reactor after filtering, the clear liquid of gained is isolated to epoxy chloropropane product, the concentrated slurry of the catalyzer of gained returns to reactor, and from clear liquid, isolated solvent and propenyl chloride also return to reactor continuation use.The method deficiency is that exothermic heat of reaction easily causes temperature of reaction to be difficult to control, and it is complicated that catalyzer reconfigures slurries process.
CN101481364B discloses a kind of continuous production method of epoxy chloropropane by hydrogen peroxide method, it is characterized in that reactor is single still, or is the slurry-bed reaction still series connection of the identical or different volume of multistage volume; Reaction solution does not need to be homogeneous phase, the pulp particle of propenyl chloride, solvent and titanium-silicon molecular sieve catalyst joins in the first reactor with volume pump, in the first reactor or every first order reaction still, drip hydrogen peroxide, reaction is carried out under solutions of weak acidity, reacting rear material carries out profit layering through relay tank, is divided into oil phase and water slurries; Catalyzer is suspended in water, and oil phase is sent into rectifying tower separating chlorine propylene and epoxy chloropropane and Trace Methanol; Water slurries after filtering, catalyzer filter cake or concentrated slurry are directly with squeezing into first step epoxidation reaction still with pump after solvent making beating, the water that after filtering, water contains methyl alcohol, a small amount of epoxy chloropropane and reaction production and the water that hydrogen peroxide is brought into, adopt negative pressure rectifying separation to go out a small amount of methyl alcohol and epoxy chloropropane, the methyl alcohol of recovery is for the configuration of catalyst slurry.The method weak point is that catalyzer filters, reconfigures operating process complexity in slurries process, the easy loss of catalyzer.
Summary of the invention
The object of the invention is to solve reaction-controlled phase transfer catalysis hydrogen peroxide oxidation propenyl chloride Direct Epoxidation and produce separation and recovery of catalyst difficulty in epoxy chloropropane prior art, the problems such as fluctuation of service, provide a kind of new propenyl chloride Direct Epoxidation to prepare the continuous production method of epoxy chloropropane, the method has that temperature of reaction is steady, technical process is simple, catalyzer without reaction by separated reslurry configuration.
In order to solve above-mentioned technical problem, the present invention adopts following technical scheme to be achieved:
A kind of propenyl chloride Direct Epoxidation is produced the method for epoxy chloropropane continuously, adopt reactor to react, by reaction raw materials propenyl chloride, aqueous hydrogen peroxide solution, catalyst pulp, or and solvent by volume pump, the opening for feed through reactor lower part is transported in reactor respectively, reactor is single reactor or series multistage reactor, reactor is Multi-stage stirring tank reactor, and stirring grade is 8-10 level; Temperature of reaction 25-95 ℃, reaction pressure 0.1-1.0MPa, reaction solution can be homogeneous phase or heterogeneous state; On reactor top, be provided with the clear liquid discharge port with built-in filter, can isolate the clear liquid that contains product, on clear liquid discharge port below, reactor middle and upper part sidewall, be provided with slurry reflux outlet, what do not filter out is refluxed and is delivered in reactor through slurry reflux entrance in reactor bottom by mashing pump containing the complete material of catalyzer unreacted, in continuous flow procedure without reclaiming catalyzer, catalyzer is without separated, filtration reslurry process, this kind of catalyst body inner loop mode simplified technical process, reduced production cost, improved working efficiency; Gas phase part is carried out condensing reflux by the condenser of reactor head.
Described reactor can be single reactor, or by pipeline series multistage reactor, staged reactor volume can be different, also can be identical;
Single reactor structure: be provided with the clear liquid discharge port containing built-in filter in reactor upper portion side wall, on clear liquid discharge port below, reactor middle and upper part sidewall, be provided with slurry reflux outlet, on the lower sides of reactor, be provided with opening for feed and slurry reflux entrance, slurry reflux outlet is connected by pipeline with slurry reflux entrance, and is provided with mashing pump on their connecting tube; Reactor head is provided with reflux exchanger;
Staged reactor consists of two above pipeline tandem reactors, and structure is: in staged reactor, each reactor head is equipped with reflux exchanger;
On the lower sides of first step reactor, be provided with opening for feed and slurry reflux entrance; On the sidewall of first step reactor middle and upper part, be provided with overflow port; In the upper portion side wall of the last stage reactor, be provided with the clear liquid discharge port containing built-in filter, on clear liquid discharge port below, reactor middle and upper part sidewall, be provided with slurry reflux outlet, slurry reflux outlet is connected by pipeline with slurry reflux entrance, and is provided with mashing pump on their connecting tube;
On every stage reactor middle and upper part sidewall before the last stage reactor, be provided with overflow port, in the second stage, to every stage reactor lower sides of the last stage reactor, be provided with overflow material inlet, the overflow port of adjacent second reactor is connected by pipeline with overflow material inlet, and material flows out from the overflow port of upper level reactor that the overflow material inlet streams through next stage reactor enters in next stage reactor by pipeline.
When propenyl chloride Direct Epoxidation is produced epoxy chloropropane employing single reactor, after reaction mass joins in reactor by volume pump, by the built-in strainer in reactor upper end, filter out and contain product clear liquid, containing the complete material of catalyzer unreacted, by volume pump, can reflux and be delivered in reactor, in continuous flow procedure without reclaiming catalyzer, gas phase part is carried out condensing reflux by the condenser of reactor top, when propenyl chloride Direct Epoxidation is produced epoxy chloropropane employing series multistage reactor, reaction mass passes through the upper end overflow of first step reactor to reactor lower end, the second stage, the built-in strainer in reactor upper end, the second stage filters out and contains product clear liquid, containing the complete material of catalyzer unreacted, by volume pump, can reflux and be delivered in first step reactor.
Reaction process is thermopositive reaction, and condenser and reaction be outside to be provided with heat that jacket for heat exchange layer can generate reaction and to carry out heat exchange and carry away, and gas phase part is carried out condensing reflux by the condenser of reactor top.
Technical process provided by the invention is applicable to have the phosphorus heteropoly tungstic acid salt catalyst that phase transition feature is controlled in reaction.
It is 5-50g/1mol that catalyzer is selected the ratio of its consumption of heteropolyacid and hydrogen peroxide; The molar ratio of propenyl chloride and hydrogen peroxide is 1-1000: 1;
Strainer need to be arranged on upper end in reactor, and strainer can adopt any one in purpose ceramic-film filter, sintered-metal filter; The particle diameter of applicable catalyzer is depended in the aperture of strainer, generally, the aperture of strainer is than the large 1-5 μ of the particle diameter of catalyzer m, product discharging method adopts reaction internal pressure higher than external pressure, clear liquid to be flowed out from strainer, and the clear liquid flowing out is carried out to product analysis and the separated data such as transformation efficiency that can obtain epoxy chloropropane selectivity and hydrogen peroxide.
The method has that temperature of reaction is steady, technical process is simple, catalyzer without reaction by separated reslurry configuration, effective utilization ratio of hydrogen peroxide is high and epoxy chloropropane yield is high feature.Can be used in industrial production.
Accompanying drawing explanation
Fig. 1 is that propenyl chloride Direct Epoxidation is produced epoxy chloropropane single reactor process flow diagram.
Fig. 2 is that propenyl chloride Direct Epoxidation is produced two reactors in series process flow diagrams of epoxy chloropropane.
Wherein 1 is propenyl chloride volume pump, and 2 is hydrogen peroxide volume pump, and 3 is catalyst pulp volume pump, and 4 is circulation slurry volume pump, and 5 is reactor, and 6 is strainer, and 7 is condenser, and 8 is solvent volume pump.
Below by specific embodiment, the present invention is further illustrated, but scope of the present invention is not limited to lifted embodiment.
Embodiment
[embodiment 1]
Press two reactors in series epichlorohydrin production process shown in Fig. 2;
Second reactor consists of two pipeline tandem reactors, and structure is: in second reactor, each reactor head is equipped with reflux exchanger;
On the lower sides of first step reactor, be provided with opening for feed and slurry reflux entrance; On the sidewall of first step reactor middle and upper part, be provided with overflow port; In the upper portion side wall of the last stage reactor, be provided with the clear liquid discharge port containing built-in filter, on clear liquid discharge port below, reactor middle and upper part sidewall, be provided with slurry reflux outlet, slurry reflux outlet is connected by pipeline with slurry reflux entrance, and is provided with mashing pump on their connecting tube;
On the sidewall of first step reactor middle and upper part, be provided with overflow port, on the last stage reactor lower sides, be provided with overflow material inlet, the overflow port of second reactor is connected by pipeline with overflow material inlet, and material flows out from the overflow port of first step reactor that the overflow material inlet streams through second stage reactor enters in the reactor of the second stage by pipeline.
Each reactor volume is 30L, amounting to volume is 60L, by 2.5kg phosphorus heteropoly tungstic acid salt catalyst, 40L propenyl chloride joins in reactor by volume pump in advance, reaching temperature of reaction, is 45 ℃, reaction pressure is 0.8MPa, start to produce continuously, propenyl chloride and hydrogen peroxide are transported in first step reactor by volume pump, and propenyl chloride feed rate is 10L/h, 50% hydrogen peroxide feed rate is 2L/h, and mixing speed is 300r/min.
Reaction mass passes through the upper end overflow of first step reactor to reactor lower end, the second stage, the built-in strainer in reactor upper end, the second stage filters out and contains product clear liquid, containing the complete material of catalyzer unreacted, by volume pump, can reflux and be delivered in first step reactor, in continuous flow procedure, without reclaiming catalyzer, gas phase part is carried out condensing reflux by the condenser of reactor top.Reaction process is thermopositive reaction, and condenser 7 and reaction be outside to be provided with heat that jacket for heat exchange layer can generate reaction and to carry out heat exchange and carry away.
Isolated clear liquid analysis is obtained to the yield of epoxy chloropropane, the transformation efficiency of the selectivity of epoxy chloropropane, hydrogen peroxide.
[embodiment 2]
Press the single reactor epichlorohydrin production process shown in Fig. 1;
Single reactor structure: be provided with the clear liquid discharge port containing built-in filter in reactor upper portion side wall, on clear liquid discharge port below, reactor middle and upper part sidewall, be provided with slurry reflux outlet, on the lower sides of reactor, be provided with opening for feed and slurry reflux entrance, slurry reflux outlet is connected by pipeline with slurry reflux entrance, and is provided with mashing pump on their connecting tube; Reactor head is provided with reflux exchanger;
Reactor volume is 45L, amounting to volume is 45L, by 2.5kg phosphorus heteropoly tungstic acid salt catalyst, 35L propenyl chloride joins in reactor by volume pump in advance, reaching temperature of reaction, is 50 ℃, reaction pressure is 0.1MPa, start to produce continuously, propenyl chloride, hydrogen peroxide are transported in first step reactor by volume pump, and propenyl chloride feed rate is 8L/h, 50% hydrogen peroxide feed rate is 2L/h, and mixing speed is 150r/min.
After reaction mass joins in reactor by volume pump, by the built-in strainer in reactor upper end, filter out and contain product clear liquid, containing the complete material of catalyzer unreacted, by volume pump, can reflux and be delivered in reactor, in continuous flow procedure without reclaiming catalyzer, gas phase part is carried out condensing reflux by the condenser of reactor top, reaction process is thermopositive reaction, and condenser 7 and reaction be outside to be provided with heat that jacket for heat exchange layer can generate reaction and to carry out heat exchange and carry away.
Isolated clear liquid analysis is obtained to the yield of epoxy chloropropane, the transformation efficiency of the selectivity of epoxy chloropropane, hydrogen peroxide.
Claims (9)
1. the method that propenyl chloride Direct Epoxidation is produced epoxy chloropropane continuously, adopt reactor (5) to react, by reaction raw materials propenyl chloride, aqueous hydrogen peroxide solution, catalyst pulp, or and solvent by volume pump, the opening for feed through reactor (5) bottom is transported in reactor (5) respectively, reactor (5) is single reactor or series multistage reactor, 25～95 ℃ of temperature of reaction, reaction pressure 0.1～1.0MPa, reaction solution can be homogeneous phase or heterogeneous state; On reactor (5) top, be provided with the clear liquid discharge port of band built-in filter (6), can isolate the clear liquid that contains product, on clear liquid discharge port below, reactor (5) middle and upper part sidewall, be provided with slurry reflux outlet, what do not filter out is refluxed and is delivered in reactor (5) through slurry reflux entrance in reactor (5) bottom by circulation slurry volume pump (4) containing the complete material of catalyzer unreacted, in continuous flow procedure, without reclaiming catalyzer, gas phase part is carried out condensing reflux by the condenser (7) of reactor head;
Described catalysts is to have the phospho heteropoly tungstate that phase transition feature is controlled in reaction.
2. method according to claim 1, is characterized in that: described reactor (5) can be single reactor, or by pipeline series multistage reactor, staged reactor volume can be different, also can be identical;
Single reactor structure: be provided with the clear liquid discharge port containing built-in filter (6) in reactor (5) upper portion side wall, on clear liquid discharge port below, reactor (5) middle and upper part sidewall, be provided with slurry reflux outlet, on the lower sides of reactor (5), be provided with opening for feed and slurry reflux entrance, slurry reflux outlet is connected by pipeline with slurry reflux entrance, and on their connecting tube, is provided with circulation slurry volume pump (4); Reactor (5) top is provided with reflux exchanger (7);
Staged reactor consists of two above pipeline tandem reactors, and structure is: in staged reactor, each reactor (5) top is equipped with reflux exchanger (7);
On the lower sides of first step reactor, be provided with opening for feed and slurry reflux entrance; On the sidewall of first step reactor middle and upper part, be provided with overflow port; In the upper portion side wall of the last stage reactor, be provided with the clear liquid discharge port containing built-in filter (6), on clear liquid discharge port below, reactor middle and upper part sidewall, be provided with slurry reflux outlet, slurry reflux outlet is connected by pipeline with slurry reflux entrance, and on their connecting tube, is provided with circulation slurry volume pump;
On every stage reactor middle and upper part sidewall before the last stage reactor, be provided with overflow port, in the second stage, to every stage reactor lower sides of the last stage reactor, be provided with overflow material inlet, the overflow port of adjacent second reactor is connected by pipeline with overflow material inlet, and material flows out from the overflow port of upper level reactor that the overflow material inlet streams through next stage reactor enters in next stage reactor by pipeline.
3. method according to claim 1 and 2, is characterized in that: described reactor (5) is Multi-stage stirring tank reactor, and stirring grade is 8～10 grades.
4. method according to claim 1, is characterized in that: the ratio of catalysts consumption and hydrogen peroxide is 5～50g/1mol; The molar ratio of propenyl chloride and hydrogen peroxide is 1～1000:1.
5. method according to claim 1, is characterized in that: temperature of reaction is 25～55 ℃, and pressure is 0.1～1.0MPa, selects rare gas element as protection gas and maintains reaction pressure.
6. method according to claim 1, is characterized in that: described built-in filter is purpose ceramic-film filter or sintered metal filtration core, little 1～5 μ m of particle diameter of the aperture ratio catalyzer of strainer; Built-in filter in described reactor is that detachable pipeline is connected with sidewall of reactor supernatant liquor discharge port mode of connection.
7. method according to claim 6, it is characterized in that: the hole of the sintered metal filtration core being equipped with in described reactor requires between 0.1～100 μ m, quantitative requirement is between 2～32, sintered metal filtration core is shaped as open circles column type, and the internal diameter of sintered metal filtration core diameter and reactor requires proportional range between 1:4～12.
8. method according to claim 1, is characterized in that: described propenyl chloride concentration requirement is more than 95%, and aqueous hydrogen peroxide solution concentration range is between 27%～75%, and solvent load is between 0～8 times of propenyl chloride quality consumption.
9. method according to claim 1 and 2, is characterized in that: react for thermopositive reaction, reactor is provided with jacket for heat exchange layer outward, and the heat that the jacket for heat exchange layer that condenser (7) and reactor outside are provided with can generate reaction carries out heat exchange and carries away.
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| CN201110424544.7A CN103159703B (en) | 2011-12-16 | 2011-12-16 | Method of continuously producing epichlorohydrin by directly epoxidizing chloropropene |
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| CN105712955B (en) * | 2014-12-05 | 2018-10-26 | 中国科学院大连化学物理研究所 | A kind of technological process of preparing epoxy chloropropane by epoxidation of propylene chloride |
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| CN111072598B (en) * | 2019-12-12 | 2023-09-29 | 中国科学院大连化学物理研究所 | Process for producing epichlorohydrin by direct oxidation of titanium-silicon molecular sieve catalyst |
| CN211771016U (en) * | 2019-12-12 | 2020-10-27 | 中国科学院大连化学物理研究所 | Device for producing epichlorohydrin by oxidizing chloropropene with titanium-silicon molecular sieve as catalyst |
| CN114539076A (en) * | 2022-03-28 | 2022-05-27 | 苏州市晶协高新电子材料有限公司 | Continuous synthesis device and process of dimethyl diallyl ammonium chloride |
| CN115894400B (en) * | 2022-12-01 | 2024-02-02 | 中国科学院大连化学物理研究所 | Process for preparing epoxy chloropropane by directly oxidizing chloropropene by using liquid-solid circulating fluidized bed reactor |
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| CN1275952C (en) * | 2003-03-28 | 2006-09-20 | 中国石油化工股份有限公司 | Production method of epoxy chloropropane |
| CN101481364B (en) * | 2009-02-24 | 2010-12-08 | 江苏扬农化工集团有限公司 | Continuous production method of epoxy chloropropane by hydrogen peroxide process |
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| DE10196976B4 (en) * | 2000-11-29 | 2006-10-26 | China Petroleum And Chemical Corporation | Reaction-Controlled Phase Transfer Catalyst-Catalyzed Oxidation Reaction Process |
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| CN1275952C (en) * | 2003-03-28 | 2006-09-20 | 中国石油化工股份有限公司 | Production method of epoxy chloropropane |
| CN101481364B (en) * | 2009-02-24 | 2010-12-08 | 江苏扬农化工集团有限公司 | Continuous production method of epoxy chloropropane by hydrogen peroxide process |
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