CN103159703A - 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 the 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, the chlorohydrination main raw material is propylene, chlorine and lime, and principal reaction technique gets propenyl chloride, propenyl chloride hypochlorination by the propylene high-temperature chlorination and gets dichlorohydrine, dichlorohydrine saponification and get three steps of epoxy chloropropane and form.Chlorohydrination process characteristic: the characteristics with production maximization, serialization and automatization, and have advantages of 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, go on foot with chlorine addition synthesizing dichloropropanol and saponification dehydrochlorination four and form.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.For seriously polluted, the problem such as equipment is perishable that solve effectively that propenyl chloride method and allyl acetate-allyl alcohol method production exists, the direct oxidation of exploitation propenyl chloride prepares the epoxy chloropropane process for cleanly preparing and arises at the historic moment.The technique that present propenyl chloride direct oxidation prepares epoxy chloropropane 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
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2)
2]
4}
3-Be catalytic active species, aqueous hydrogen peroxide solution is oxygenant, and benzene is solvent, and the productive rate of epoxy chloropropane is 85% after reacting 2.5 hours.CN1298876 discloses a kind of method of preparing epoxy chloropropane by catalytic epoxidation of chloropropene by molecular oxygen, take molecular oxygen as oxygenant, the transition metal heteropolyacid salt is catalyzer, and the relative traditional technology of the 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 catalysis hydrogen peroxide direct oxidation propenyl chloride epoxy chloropropane processed preferably, solid but due to the own solid-liquid of catalyzer in its reaction process-the phase transition characteristics, 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 the 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 prepares epoxy chloropropane, take HTS as catalyzer, hydrogen peroxide is oxygenant, the 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 cause environmental pollution, but because catalyst Ti-si molecular sieves needs to 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 the 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 that catalyzer is improved, 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, simultaneously 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.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 the partial material pressurization, circulation enters reactor, partial material is sent separator, the epoxy chloropropane that goes out after separation is sent to refiningly, and the slurry that contains catalyzer returns to material-compound tank to be continued to use.The method is not owing to using solvent, and catalyzer is bad dispersibility in reaction process, and the activity of catalyzer and life-span can affect adversely, and catalyst separating adopts the spinning liquid isolation technique in addition, the operating process very complicated, is unfavorable for industrial production.
CN101172970A discloses a kind of method of producing epoxy chloropropane, and take HTS as catalyzer, take hydrogen peroxide as oxygenant, take acetonitrile as solvent, take fixed bed as reactor, the 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, the duct is easily stopped up in addition, easily cause productive rate low, in reaction process, heat release concentrates on beds, causes easily that in production process, by-product increases, selectivity descends.
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 the epoxy chloropropane product, the concentrated slurry of the catalyzer of gained returns to reactor, and isolated solvent and propenyl chloride also return to reactor continuation use from clear liquid.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 the 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, drip hydrogen peroxide in the first reactor or every first order reaction still, reaction is carried out under solutions of weak acidity, reacting rear material carries out the profit layering through relay tank, is divided into oil phase and water slurries; Catalyzer is suspended in aqueous phase, and oil phase is sent into rectifying tower separating chlorine propylene and epoxy chloropropane and Trace Methanol; The water slurries after filtering, catalyzer filter cake or concentrated slurry are directly with squeezing into first step epoxidation reaction still with pump after the solvent making beating, after filtering, water contains the water of methyl alcohol, a small amount of epoxy chloropropane and reaction production and the water that hydrogen peroxide is brought into, adopt the negative pressure rectifying separation to go out a small amount of methyl alcohol and epoxy chloropropane, the methyl alcohol of recovery is used for the configuration of catalyst slurry.The method weak point is that catalyzer filters, reconfigures operating process complexity in the 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 on the 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 need not reaction by separating the 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, with reaction raw materials propenyl chloride, aqueous hydrogen peroxide solution, catalyst pulp, or and solvent be transported in reactor by the opening for feed of volume pump through reactor lower part respectively, reactor is single reactor or series multistage reactor, reactor is the Multi-stage stirring tank reactor, and stirring grade is the 8-10 level; Temperature of reaction 25-95 ℃, reaction pressure 0.1-1.0MPa, reaction solution can be homogeneous phase or heterogeneous state; Be provided with the clear liquid discharge port with built-in filter on reactor top, can isolate the clear liquid that contains product, be provided with the slurry reflux outlet on the sidewall of clear liquid discharge port below, reactor middle and upper part, the complete material of catalyzer unreacted that contains that does not filter out refluxes through the slurry reflux entrance in the reactor bottom by mashing pump and is delivered to reactor, need not to reclaim catalyzer in continuous flow procedure, catalyzer need not to separate, filter the reslurry process, this kind catalyst body inner loop mode has been simplified technical process, has been reduced production cost, has improved working efficiency; The 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, the staged reactor volume can be different, also can be identical;
Single reactor structure: be provided with the clear liquid discharge port that contains built-in filter on the reactor upper portion side wall, be provided with the slurry reflux outlet on the sidewall of clear liquid discharge port below, reactor middle and upper part, be provided with opening for feed and slurry reflux entrance on the lower sides of reactor, the slurry reflux outlet connects by pipeline with the slurry reflux entrance, and is provided with mashing pump on their connecting tube; Reactor head is provided with reflux exchanger;
Staged reactor is made of two above pipeline tandem reactors, and structure is: in staged reactor, each reactor head is equipped with reflux exchanger;
Be provided with opening for feed and slurry reflux entrance on the lower sides of first step reactor; Be provided with overflow port on the sidewall of first step reactor middle and upper part; Be provided with the clear liquid discharge port that contains built-in filter on the upper portion side wall of the last stage reactor, be provided with the slurry reflux outlet on the sidewall of clear liquid discharge port below, reactor middle and upper part, the slurry reflux outlet connects by pipeline with the slurry reflux entrance, and is provided with mashing pump on their connecting tube;
Be provided with overflow port on the every stage reactor middle and upper part sidewall before the last stage reactor, be provided with the overflow material inlet in the second stage to every stage reactor lower sides of the last stage reactor, the overflow port of adjacent second reactor connects by pipeline with the overflow material inlet, and material flows out to enter in the next stage reactor by the overflow material inlet streams of pipeline through the next stage reactor from the overflow port of upper level reactor.
when the propenyl chloride Direct Epoxidation is produced epoxy chloropropane employing single reactor, after reaction mass joins in reactor by volume pump, filter out by the built-in strainer in reactor upper end and contain the product clear liquid, containing the complete material of catalyzer unreacted can reflux by volume pump and be delivered in reactor, need not to reclaim catalyzer in continuous flow procedure, the gas phase part is carried out condensing reflux by the condenser of reactor top, when the 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 the product clear liquid, containing the complete material of catalyzer unreacted can reflux by volume pump and be delivered in first step reactor.
Reaction process is thermopositive reaction, and condenser and reaction be outside to be provided with the jacket for heat exchange layer and the heat that reaction generates can be carried out heat exchange and carry away, and the 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 the phase transition characteristics are 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 the catalyzer that is suitable for is depended in the aperture of strainer, generally, the aperture of strainer is than the large 1-5 μ of the particle diameter m of catalyzer, the product discharging method adopts the reaction internal pressure to make clear liquid flow out from strainer higher than external pressure, and the clear liquid that flows out is carried out product analysis and separates the 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 need not to react by separating reslurry configuration, effective utilization ratio of hydrogen peroxide is high and the epoxy chloropropane yield is high characteristics.Can be used in industrial production.
Description of drawings
Fig. 1 is that the propenyl chloride Direct Epoxidation is produced epoxy chloropropane single reactor process flow diagram.
Fig. 2 is that the propenyl chloride Direct Epoxidation is produced two reactors in series process flow diagrams of epoxy chloropropane.
Wherein 1 is the propenyl chloride volume pump, and 2 is the hydrogen peroxide volume pump, and 3 is the catalyst pulp volume pump, and 4 are circulation slurry volume pump, and 5 is reactor, and 6 is strainer, and 7 is condenser, and 8 is the solvent volume pump.
The present invention is further illustrated below by specific embodiment, but scope of the present invention be not limited to for embodiment.
Embodiment
[embodiment 1]
By two reactors in series epichlorohydrin production process shown in Figure 2;
Second reactor is made of two pipeline tandem reactors, and structure is: in second reactor, each reactor head is equipped with reflux exchanger;
Be provided with opening for feed and slurry reflux entrance on the lower sides of first step reactor; Be provided with overflow port on the sidewall of first step reactor middle and upper part; Be provided with the clear liquid discharge port that contains built-in filter on the upper portion side wall of the last stage reactor, be provided with the slurry reflux outlet on the sidewall of clear liquid discharge port below, reactor middle and upper part, the slurry reflux outlet connects by pipeline with the slurry reflux entrance, and is provided with mashing pump on their connecting tube;
Be provided with overflow port on the sidewall of first step reactor middle and upper part, be provided with the overflow material inlet on the last stage reactor lower sides, the overflow port of second reactor connects by pipeline with the overflow material inlet, and material flows out to enter in the reactor of the second stage by the overflow material inlet streams of pipeline through second stage reactor from the overflow port of first step reactor.
Each reactor volume is 30L, amounting to volume is 60L, with 2.5kg phosphorus heteropoly tungstic acid salt catalyst, the 40L propenyl chloride joins in reactor by volume pump in advance, is 45 ℃ reaching temperature of reaction, reaction pressure is 0.8MPa, beginning is produced continuously, and propenyl chloride and hydrogen peroxide are transported in first step reactor by volume pump, and the 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 the product clear liquid, containing the complete material of catalyzer unreacted can reflux by volume pump and be delivered in first step reactor, need not to reclaim catalyzer in continuous flow procedure, the 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 the jacket for heat exchange layer and the heat that reaction generates can be carried out heat exchange and carry away.
Isolated clear liquid analysis is obtained the yield of epoxy chloropropane, the selectivity of epoxy chloropropane, the transformation efficiency of hydrogen peroxide.
[embodiment 2]
By single reactor epichlorohydrin production process shown in Figure 1;
Single reactor structure: be provided with the clear liquid discharge port that contains built-in filter on the reactor upper portion side wall, be provided with the slurry reflux outlet on the sidewall of clear liquid discharge port below, reactor middle and upper part, be provided with opening for feed and slurry reflux entrance on the lower sides of reactor, the slurry reflux outlet connects by pipeline with the 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, with 2.5kg phosphorus heteropoly tungstic acid salt catalyst, the 35L propenyl chloride joins in reactor by volume pump in advance, is 50 ℃ reaching temperature of reaction, reaction pressure is 0.1MPa, beginning is produced continuously, and propenyl chloride, hydrogen peroxide are transported in first step reactor by volume pump, and the 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, filter out by the built-in strainer in reactor upper end and contain the product clear liquid, containing the complete material of catalyzer unreacted can reflux by volume pump and be delivered in reactor, need not to reclaim catalyzer in continuous flow procedure, the 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 the jacket for heat exchange layer and the heat that reaction generates can be carried out heat exchange and carry away.
Isolated clear liquid analysis is obtained the yield of epoxy chloropropane, the selectivity of epoxy chloropropane, the transformation efficiency of hydrogen peroxide.
Claims (9)
1. method that the propenyl chloride Direct Epoxidation is produced epoxy chloropropane continuously, adopt reactor (5) to react, with reaction raw materials propenyl chloride, aqueous hydrogen peroxide solution, catalyst pulp, or and solvent be transported in reactor (5) by the opening for feed of volume pump through reactor (5) bottom respectively, reactor (5) is single reactor or series multistage reactor, temperature of reaction 25-95 ℃, reaction pressure 0.1-1.0MPa, reaction solution can be homogeneous phase or heterogeneous state; be provided with the clear liquid discharge port of band built-in filter (6) on reactor (5) top, can isolate the clear liquid that contains product, in clear liquid discharge port below, be provided with the slurry reflux outlet on the sidewall of reactor (5) middle and upper part, the complete material of catalyzer unreacted that contains that does not filter out refluxes through the slurry reflux entrance in reactor (5) bottom by circulation slurry volume pump (4) and is delivered to reactor (5), need not to reclaim catalyzer in continuous flow procedure, the gas phase part is carried out condensing reflux by the condenser (7) of reactor head.
2. method according to claim 1, it is characterized in that: described reactor (5) can be single reactor, or by pipeline series multistage reactor, the staged reactor volume can be different, also can be identical;
Single reactor structure: be provided with the clear liquid discharge port that contains built-in filter (6) on reactor (5) upper portion side wall, be provided with the slurry reflux outlet on the sidewall of clear liquid discharge port below, reactor (5) middle and upper part, be provided with opening for feed and slurry reflux entrance on the lower sides of reactor (5), the slurry reflux outlet connects by pipeline with the slurry reflux entrance, and is provided with circulation slurry volume pump (4) on their connecting tube; Reactor (5) top is provided with reflux exchanger (7);
Staged reactor is made of two above pipeline tandem reactors, and structure is: in staged reactor, each reactor (5) top is equipped with reflux exchanger (7);
Be provided with opening for feed and slurry reflux entrance on the lower sides of first step reactor; Be provided with overflow port on the sidewall of first step reactor middle and upper part; Be provided with the clear liquid discharge port that contains built-in filter (6) on the upper portion side wall of the last stage reactor, be provided with the slurry reflux outlet on the sidewall of clear liquid discharge port below, reactor middle and upper part, the slurry reflux outlet connects by pipeline with the slurry reflux entrance, and is provided with circulation slurry volume pump on their connecting tube;
Be provided with overflow port on the every stage reactor middle and upper part sidewall before the last stage reactor, be provided with the overflow material inlet in the second stage to every stage reactor lower sides of the last stage reactor, the overflow port of adjacent second reactor connects by pipeline with the overflow material inlet, and material flows out to enter in the next stage reactor by the overflow material inlet streams of pipeline through the next stage reactor from the overflow port of upper level reactor.
3. method according to claim 1 and 2, it is characterized in that: described reactor (5) is the Multi-stage stirring tank reactor, stirring grade is the 8-10 level.
4. method according to claim 1 is characterized in that: described catalysts is to have the phospho heteropoly tungstate that the phase transition characteristic is controlled in reaction; It is 5-50g/1mol that catalysts is selected the ratio of its consumption of phospho heteropoly tungstate and hydrogen peroxide; The molar ratio of propenyl chloride and hydrogen peroxide is 1-1000: 1.
5. method according to claim 1, it 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 keeps reaction pressure.
6. method according to claim 1, it is characterized in that: described built-in filter is purpose ceramic-film filter or sintered metal filtration core, the little 1-5 μ of the particle diameter m 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 that is equipped with in described reactor requires between 0.1-100 μ m, quantitative requirement is between 2-32, the sintered metal filtration core is shaped as the open circles column type, and the internal diameter of sintered metal filtration core diameter and reactor requires proportional range 1: between 4-12.
8. method according to claim 1, it is characterized in that: described propenyl chloride concentration requirement is more than 95%, the aqueous hydrogen peroxide solution concentration range between 27%-75%, solvent load be propenyl chloride quality consumption 0-8 doubly between.
9. method according to claim 1 and 2, it is characterized in that: react and be thermopositive reaction, be provided with the jacket for heat exchange layer outside establishing reactor, the jacket for heat exchange layer that condenser (7) and reactor outside are provided with can carry out heat exchange with the heat that reaction generates and carry away.
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| CN103351366A (en) * | 2013-07-01 | 2013-10-16 | 太仓市恒益医药化工原料厂 | Method for continuous production of epoxy chloropropane through reaction-separation coupling |
| CN105712955A (en) * | 2014-12-05 | 2016-06-29 | 中国科学院大连化学物理研究所 | Technical process for producing epichlorohydrin by chloropropene epoxidation |
| CN106117121A (en) * | 2016-08-17 | 2016-11-16 | 南京红太阳生物化学有限责任公司 | A kind of device and method of synthesis 2,2 bipyridyls |
| CN106967010A (en) * | 2016-01-13 | 2017-07-21 | 中国石油化工股份有限公司 | A kind of chloropropene method for oxidation |
| CN108395418A (en) * | 2018-04-10 | 2018-08-14 | 江苏扬农化工集团有限公司 | A kind of technique that chloropropene Direct Epoxidation prepares epoxychloropropane |
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| CN109912541A (en) * | 2019-02-26 | 2019-06-21 | 山东凯泰科技股份有限公司 | A kind of realized using phase transfer catalyst directly produces ECH continuous production commercial run |
| CN110078683A (en) * | 2019-05-20 | 2019-08-02 | 江苏扬农化工集团有限公司 | A kind of epoxychloropropane is continuously synthesizing to technique |
| CN111057026A (en) * | 2019-12-12 | 2020-04-24 | 中国科学院大连化学物理研究所 | Method for continuously producing epichlorohydrin by catalyzing and oxidizing chloropropene with titanium-silicon molecular sieve |
| CN111072598A (en) * | 2019-12-12 | 2020-04-28 | 中国科学院大连化学物理研究所 | Process for producing epichlorohydrin by direct oxidation of titanium silicalite molecular sieve catalyst |
| CN111116520A (en) * | 2019-12-12 | 2020-05-08 | 中国科学院大连化学物理研究所 | Process for producing epichlorohydrin by using titanium silicalite molecular sieve as catalyst to oxidize chloropropene |
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| 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 |
| WO2024113592A1 (en) * | 2022-12-01 | 2024-06-06 | 中国科学院大连化学物理研究所 | Process for preparing epichlorohydrin by directly oxidizing chloropropene by using liquid-solid circulating fluidized bed reactor |
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