CN110357835A - A kind of preparation method of epichlorohydrin - Google Patents
A kind of preparation method of epichlorohydrin Download PDFInfo
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- CN110357835A CN110357835A CN201910823367.6A CN201910823367A CN110357835A CN 110357835 A CN110357835 A CN 110357835A CN 201910823367 A CN201910823367 A CN 201910823367A CN 110357835 A CN110357835 A CN 110357835A
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a kind of preparation methods of epichlorohydrin, including reaction workshop section, washing room, refinement, simple process is environmentally protective, the recycling of catalyst can be achieved, it is low to efficiently solve catalyst activity, stability is poor, service life short problem, cost performance is high, the problem of effectively preventing frequent driving and parking significantly reduces production cost, has wide industrial applications prospect.
Description
Technical field
The invention belongs to organic chemicals synthesis technical fields, more particularly, to a kind of preparation method of epichlorohydrin.
Background technique
Epichlorohydrin, also known as epoxychloropropane (ECH) are a kind of colourless liquids, not soluble in water, and being is large organic chemical industry
Raw material and fine chemical product are the third-largest epoxides that yield is only second to ethylene oxide and propylene oxide, are widely used in
Produce the fields such as epoxy resin, synthetic glycerine and chlorohydrin rubber, it can also be used to prepare other derivatives, also act as solvent, increase
Agent, fire retardant and surfactant etc. are moulded, is the important intermediate of a kind of important Organic Chemicals and petrochemical industry.
Currently, the industrial process of epoxychloropropane in the world, mainly there is propylene high-temperature chloridising, propylene acetate method
With 3 kinds of glycerin chlorination saponification method.Wherein, propylene high-temperature chloridising is domestic and international most important production method.At this stage, with propylene
Account for about the 90% of total output for the propylene high-temperature chloridising of raw material, glycerin chlorination saponification method accounts for the 10% of total output, acetic acid propylene
Ester process is eliminated substantially.Propylene high-temperature chloridising has production flexibly, the more mature technical advantage of technique, but its yield
Low, energy consumption is high, equipment seriously corroded and " three wastes " discharge amount is big.
For the technological deficiency for solving propylene high-temperature chloridising, US4833260 discloses one kind for the first time with Titanium Sieve Molecular Sieve and is
Catalyst, hydrogen peroxide are oxidant, directly carry out epoxidation to alkene and produce epoxides method.This method reaction condition temperature
With environmentally protective, by-product only has water.But since there are intensive polar solvents in reaction system, epoxides is caused to be easy open loop
Ethers by-product is generated, so that the selectivity of epoxides only has 85% or so, yield is lower.In addition, there is also urge for this method
Agent service life shorter critical issue.
For the yield for further increasing epoxides, patent US4824976, CN1319099A discloses a kind of acid neutralization
The method that agent is in advance modified Ti-Si catalyst, by with sodium hydroxide, the alkaline matters such as ammonium hydroxide to Titanium Sieve Molecular Sieve into
Row is modified, can the acidic-group in catalyst neutralisation surface and duct improve epoxides choosing to inhibit the generation of side reaction
Selecting property.But catalyst use cost further increases, and is unfavorable for Atom economy.In addition, patent US5646314 and
US5675026, which is disclosed, is modified to Ti-Si catalyst using alkaline assistant or is added in the reaction system micro basic species
Matter condition pH value inhibits the progress of side reaction, improves the selectivity of epoxides.But the introducing of alkaline matter, it will cause double
Oxygen water electrode is unstable, causes its decomposition, increases operational danger.It should be noted that the above patent does not propose to be catalyzed
Agent service life short solution.
Patent CN101486690B discloses a kind of method of preparing epichlorohydrin by chloropropene epoxidation, technical characteristic
It is that a small amount of methanol is added and makees solvent, reaction solution is in split-phase state, in the condition being sufficiently stirred in autoclave/slurry bed reactor
Under, micron order catalyst is highly dispersed in oily phase and water phase, and three, which are in contact, carries out epoxidation reaction generation epoxychloropropane.By
It is in alcoholic solvent dosage few, it is soluble in the aqueous phase, a large amount of epoxychloropropane distribution avoid alcohol, water and epoxychloropropane in oily phase
By-product generation is tended to have when separation, oil is mutually separated by atmospheric distillation, and epoxychloropropane separation yield is high.But due to reactant
System is divided into water-oil phase, causes concentration of substrate excessively high, compared with homogeneous system, reacts more violent, is difficult to control.In addition, molten
The effect of agent methanol in the reaction system is not only that chloropropene is promoted to be mutually dissolved with hydrogen peroxide, eliminates diffusional resistance, and
Affect catalytic action process.For the epoxidation reaction of alkene and hydrogen peroxide, the catalytic mechanism of TS-1 is commonly considered as five yuan
Ring mechanism.When without using organic solvent, the water in hydrogen peroxide solution acts as solvent, due to the five-membered ring transition state activity of generation
Species are unstable, prevent TS-1 is acted on from giving full play to.In addition, chloropropene does not dissolve mutually with hydrogen peroxide, also affect
Reactivity, therefore the technique is lacked there are the conversion ratio of hydrogen peroxide with effective rate of utilization is not high and catalyst life is short technology
It falls into.
Patent CN1249042C discloses a kind of Suspend catalytic distillation process of direct olefin epoxidation.Its feature exists
Enter the conversion zone of destilling tower together in titanium-silicon molecular sieve catalyst, solvent, hydrogen peroxide and alkene, catalyst and liquid material are mixed
The flowing in tower is closed to be reacted to be catalyzed material.Using exothermic heat of reaction by alkene gasification separation, solvent is recycled, catalysis
After separation, gained catalyst circulation is returned conversion zone and is used for agent and unvaporized liquid material, and epoxides is from tower top or tower reactor
It is isolated in material.This method utilization of Heat of Reaction rate is high, and energy consumption is greatly reduced, can effectively inhibit side reaction.But
This method equally exists the shorter problem of catalyst life, and with the recycling of catalyst, it may appear that catalyst blocks up tower
Problem.
Summary of the invention
In view of this, the present invention is intended to provide a kind of preparation method of epichlorohydrin, effectively solution catalyst life is short, volatile
Problem living.By the way that the catalyst pulp for separating concentration after reaction is carried out purification and washing online, removing is adsorbed on catalysis in time
Agent surface and internal larger molecular organics, evacuate catalyst duct, so that catalyst stability is good, deactivation prob is not present,
Circular economy avoids the operation such as frequent driving and parking.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of preparation method of epichlorohydrin, specifically comprises the following steps:
Step 1: addition chloropropene, hydrogen peroxide and the pH adjusting agent of continuous and quantitative into reactor, while by catalyst with
It is added in reactor and is reacted together after solvent mixing, obtain the mixed liquor containing epichlorohydrin；
Step 2: the mixed liquor containing epichlorohydrin that step 1 obtains carries out separation concentration by separator, obtains catalyst
Slurry and clear liquid；
Step 3: the catalyst pulp that step 2 obtains enters in washing kettle to be washed with detergent, is purified
Catalyst and clear liquid containing a small amount of epichlorohydrin, the catalyst after washing, purifying recycles after separator recycles is driven into reactor
In；
Step 4: the clear liquid containing a small amount of epichlorohydrin that the clear liquid and step 3 that step 2 obtains obtain enters subsequent rectifying work
Duan Jinhang product purification obtains epichlorohydrin product, and unreacted chloropropene and solvent directly return to reaction after separation in clear liquid
It is recycled in device.
Above-mentioned preparation process includes on-line continuous washing, purifying process, washs to remove to be adsorbed on online by catalyst and urge
Agent surface and internal larger molecular organics, the catalyst Returning reactor after washing, purifying, therefore there is no inactivations for catalyst
Problem solves the problems, such as that catalyst life is short, stability is poor, avoids frequent driving and parking operation.
Further, the molar ratio of chloropropene and hydrogen peroxide is 1: 1~30: 1 in step 1 reactor, solvent and chlorine
The molar ratio of propylene is 3: 1~30: 1；
The mass concentration of catalyst reactor is 2~30%, and the mass concentration of catalyst is 1~50% in washing kettle.
Preferably, the molar ratio of chloropropene and hydrogen peroxide is 3: 1 in step 1 reactor；Preferably, solvent and chloropropene
Molar ratio is 4: 1；Preferably, the mass concentration of catalyst reactor is 10%；Preferably, in washing kettle catalyst quality
Concentration is 10%.
Further, the solvent is acetonitrile and low-carbon alcohols.Wherein low-carbon alcohols is methanol, ethyl alcohol, isopropanol or uncle
Butanol etc..The solvent is preferably methanol.
Further, the pH adjusting agent is ammonium hydroxide, methylamine, dimethylamine, trimethylamine, ethamine, one of triethylamine.Step
PH value of reaction system in rapid 1 is controlled in 6-7, and the pH adjusting agent is preferably ammonium hydroxide, has good economy.
Further, the catalyst are as follows:
Molecular sieve or zeolitic catalyst, with 10~500 Si: Ti molar ratio；
Or be amorphous substance catalyst, corresponding empirical formula is (TiO2)X(SiO2)1-X, wherein X value between 0.0001~
Between 0.5.
The catalyst is the catalyst of titaniferous, can be crystal (zeolite), is also possible to amorphous substance or its mixing
Object.Crystal refers mainly to the various zeolite molecular sieves of titaniferous, such as has the titaniferous of the MFI topological structure similar to ZSM-5 zeolite
Zeolite (i.e. TS-1) similar to the titanium-containing zeolite (i.e. TS-2) of the MEL topological structure of ZSM-11 zeolite, and has β zeolite, silk
Geolyte (natural or artificial synthesized), molecular sieve containing titanium of ZSM-12, MCM-22, ZSM-48 structure etc.；Amorphous substance refers mainly to
The random oxide of titaniferous, duct rule mesopore molecular sieve and duct, such as with MCM-41, SBA-15 isomorphism titaniferous material
Material and silicon dioxide carried titanium dioxide.Preferably, Si: Ti molar ratio of the molecular sieve and zeolitic catalyst be 10~
200.Preferably, amorphous substance catalyst, which has, corresponds to empirical formula (TiO2)X(SiO2)1-X, wherein X value is 0.01~0.125.
Further, the catalyst is catalyst raw powder, or catalyst by spraying, after extrusion granulation, catalyst are average
Partial size is 0.15~100 μm.Preferably, the catalyst average grain diameter is 0.2~0.4 μm.
Further, the mass concentration of the hydrogen peroxide is 27.5%, 50% or 70%.Preferably, the quality of hydrogen peroxide
Concentration is 27.5%, to improve the safety used.
Further, the detergent is made of one or both of methanol, alkyl phenol polyoxyethylene ether.Preferably,
The detergent is methanol and alkyl phenol polyoxyethylene ether mixture, wherein alkyl phenol polyoxyethylene ether mass concentration 0.1%-
1%, preferably 0.3%-0.5%.Methanol and the mixture of alkyl phenol polyoxyethylene ether can effectively promote catalyst as detergent
Cleaning effect, and then catalyst reaction activity and reaction efficiency are promoted, keep reaction more abundant.
Further, the operating condition of the reaction are as follows: 30~110 DEG C of reaction temperature, reaction pressure normal pressure~3.0MPa,
10~60min of reaction time, 30~200 DEG C of catalyst detergent temperature, 2~72h of wash time.Reaction temperature is preferably 50
℃；Reaction pressure is preferably 0.3MPa；Reaction time is preferably 20min；Catalyst detergent temperature is preferably 180 DEG C；It washes
Washing the time is preferably 48h.
Further, the reactor is paste state bed reactor, and the paste state bed reactor is that circulation flow reactor or band stir
Mix the curing kettle of device.Reactor is preferably slurry bed system curing kettle.
Compared with the existing technology, a kind of preparation method of epichlorohydrin of the present invention has the advantage that
(1) present invention by carrying out purification and washing for the catalyst pulp for separating concentration after reaction online, and removing is inhaled in time
It is attached to catalyst surface and internal larger molecular organics, evacuates catalyst duct, so that catalyst stability is good, there is no lose
Problem living, need to only add trace catalyst, and circular economy avoids the operation such as frequent driving and parking.
(2) present invention is environmentally protective, and process flow is short, and using low-carbon alcohols as solvent, one side system material is in uniform
Property, reaction efficiency is improved, reactivity is high, reacts more abundant；The evaporation of another aspect solvent can be taken off reaction heat, be easy control
Reaction temperature processed.
(3) present invention uses slurry bed reactor, and the heat generated in reaction process is easily withdrawn in time, it is ensured that entire reaction
Process temperature homogeneity, and the catalyst material returned is easy to operate.
Detailed description of the invention
The attached drawing for constituting a part of the invention is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is the preparation technology flow chart of epichlorohydrin described in the embodiment of the present invention 2~11.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.
Embodiment 1 (comparative example):
This embodiment is that catalyst does not carry out continuous online washing, purifying.
Firstly, using TS-1 original powder for catalyst, catalyst average grain diameter is 0.2~0.4 μm, after mixing with methanol solvate
It is added in slurry bed system curing kettle reactor and is stirred together.Secondly, into reactor it is quantitative continuous be added chloropropene,
27.5% hydrogen peroxide and ammonium hydroxide, adjusting pH value of reaction system is 6~7.The molar ratio of chloropropene and hydrogen peroxide be 3: 1, methanol with
The molar ratio of chloropropene is 4: 1, and the mass concentration of TS-1 catalyst is 10% in reactor.Reaction condition is reaction temperature 50
DEG C, reaction pressure 0.3MPa, reaction time 20min sufficiently obtain the product mixture containing epichlorohydrin after reaction, through dividing
It is concentrated from device, obtains catalyst slurry and clear liquid, clear liquid goes subsequent rectification section to be refining to obtain epichlorohydrin product, not anti-in clear liquid
The chloropropene and solvent answered continue to be recycled in direct Returning reactor after separation, and the catalyst pulp after concentration is also again
It enters in curing kettle reactor and is recycled.Data are as shown in table 1.
Table 1:
Catalyst does not carry out continuous online washing, purifying it can be seen from embodiment 1 (comparative example), stability compared with
Difference, the service life is short, runs active sharp fall after 1000h.
Embodiment 2:
This embodiment is that catalyst carries out continuous online washing, purifying.
Firstly, using TS-1 original powder for catalyst, catalyst average grain diameter is 0.2~0.4 μm, after mixing with methanol solvate
It is added in slurry bed system curing kettle reactor and is stirred together.Secondly, into reactor it is quantitative continuous be added chloropropene,
27.5% hydrogen peroxide and ammonium hydroxide, adjusting pH value of reaction system is 6~7.The molar ratio of chloropropene and hydrogen peroxide be 3: 1, methanol with
The molar ratio of chloropropene is 4: 1, and the mass concentration of TS-1 catalyst is 10% in reactor.Reaction condition is reaction temperature 50
DEG C, reaction pressure 0.3MPa, reaction time 20min sufficiently obtain the product mixture containing epichlorohydrin after reaction, through dividing
Catalyst pulp and clear liquid are concentrated to get from device.Clear liquid goes subsequent rectification section to be refining to obtain epichlorohydrin net product, in clear liquid not
The chloropropene and solvent of reaction continue to be recycled in direct Returning reactor after separation.Catalyst pulp after concentration enters
Purification and washing, alkyl phenol polyoxyethylene ether mass concentration are carried out with methanol and alkyl phenol polyoxyethylene ether mixture into washing kettle
0.3%~0.5%, to remove the larger molecular organics being adsorbed on inside catalyst surface and duct, the catalyst being purified
With the clear liquid for containing a small amount of epichlorohydrin, purified catalyst recycles after separator recycles be driven into reactor again, washs
The mass concentration of catalyst is 10% in kettle, and 180 DEG C of catalyst detergent temperature, wash time 48h contains the clear of a small amount of epichlorohydrin
Liquid enters rectification section and carries out purification purification.Data are as shown in table 2.
Table 2:
Catalyst carries out continuous online washing, purifying it can be seen from embodiment 2, and stability is high, and activity is strong, operation
Activity is consistent with fresh catalyst after 8000h.
Embodiment 3:
Embodiment 2 is repeated, only feed change charging proportion and reaction condition.Wherein, mole of chloropropene and hydrogen peroxide
Than being 1: 1, the molar ratio of methanol and chloropropene is 3: 1, and the mass concentration of TS-1 catalyst is 2% in reactor.Reaction condition
It is as follows: 30 DEG C of reaction temperature, normal pressure, reaction time 10min.Catalyst detergent condition is as follows: catalyst in washing kettle
Mass concentration is 1%, and 30 DEG C of temperature, wash time 2h, data are as shown in table 3:
Table 3:
Embodiment 4:
Embodiment 2 is repeated, only feed change charging proportion and reaction condition.Wherein, mole of chloropropene and hydrogen peroxide
Than being 1: 1, the molar ratio of methanol and chloropropene is 30: 1, and the mass concentration of TS-1 catalyst is 30% in reactor.React item
Part is as follows: 110 DEG C of reaction temperature, reaction pressure 3.0MPa, reaction time 60min.Catalyst detergent condition is as follows: washing
The mass concentration of catalyst is 50% in kettle, and 200 DEG C of temperature, wash time 72h, data are as shown in table 4:
Table 4:
Embodiment 5:
Embodiment 2 is repeated, maintains charge ratio and reaction condition constant, only uses TS-2 original powder for catalyst, quality point
Several 50% hydrogen peroxide are oxidant, and data are as shown in table 5:
Table 5:
Embodiment 6:
Embodiment 2 is repeated, maintains charge ratio and reaction condition constant, only uses TiO2Powder is catalyst, and data are such as
Shown in table 6:
Table 6:
Embodiment 7:
Embodiment 2 is repeated, maintains charge ratio and reaction condition constant, only catalyst is the TS-1 after mist projection granulating, is urged
Agent average grain diameter is 40 μm, and data are as shown in table 7:
Table 7:
Embodiment 8:
Embodiment 2 is repeated, solvent methanol is only replaced with into acetonitrile, data are as shown in table 8:
Table 8:
Embodiment 9:
Embodiment 2 is repeated, pH adjusting agent ammonium hydroxide is only replaced with into trimethylamine, data are as shown in table 9:
Table 9:
Embodiment 10:
Embodiment 2 is repeated, slurry bed system curing kettle reactor is only replaced with into fixed-bed column reactor, TS-1 original powder is replaced
It is changed to TS-1 extruded catalyst, data are as shown in table 10:
Table 10:
Embodiment 11:
Embodiment 2 is repeated, detergent methanol and alkyl phenol polyoxyethylene ether mixture are only replaced with into methanol, data are such as
Shown in table 11:
Table 11:
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of epichlorohydrin, it is characterised in that: specifically comprise the following steps:
Step 1: addition chloropropene, hydrogen peroxide and the pH adjusting agent of continuous and quantitative into reactor, while by catalyst and solvent
It is added in reactor and is reacted together after mixing, obtain the mixed liquor containing epichlorohydrin；
Step 2: the mixed liquor containing epichlorohydrin that step 1 obtains carries out separation concentration by separator, obtains catalyst pulp
And clear liquid；
Step 3: the catalyst pulp that step 2 obtains enters in washing kettle to be washed with detergent, the catalysis being purified
Agent and clear liquid containing a small amount of epichlorohydrin, the catalyst after washing, purifying recycles after separator recycles to be driven into reactor；
Step 4: the clear liquid containing a small amount of epichlorohydrin that the clear liquid and step 3 that step 2 obtains obtain enter subsequent rectification section into
Row product purification obtains epichlorohydrin product, and unreacted chloropropene and solvent are after separation in direct Returning reactor in clear liquid
It is recycled.
2. a kind of preparation method of epichlorohydrin according to claim 1, it is characterised in that: chlorine in step 1 reactor
The molar ratio of propylene and hydrogen peroxide is 1:1~30:1, and the molar ratio of solvent and chloropropene is 3:1~30:1；
The mass concentration of catalyst reactor is 2~30%, and the mass concentration of catalyst is 1~50% in washing kettle.
3. a kind of preparation method of epichlorohydrin according to claim 1, it is characterised in that: the solvent is acetonitrile and low-carbon
Alcohols.
4. a kind of preparation method of epichlorohydrin according to claim 1, it is characterised in that: the pH adjusting agent be ammonium hydroxide,
Methylamine, dimethylamine, trimethylamine, ethamine, one of triethylamine.
5. a kind of preparation method of epichlorohydrin according to claim 1, it is characterised in that: the catalyst are as follows:
Molecular sieve or zeolitic catalyst, with 10~500 Si:Ti molar ratio；
Or be amorphous substance catalyst, corresponding empirical formula is (TiO2)X(SiO2)1-X, wherein X value is between 0.0001~0.5
Between.
6. a kind of preparation method of epichlorohydrin according to claim 1, it is characterised in that: the catalyst is catalysagen
Powder, or catalyst spraying, after extrusion granulation, catalyst average grain diameter is 0.15~100 μm.
7. a kind of preparation method of epichlorohydrin according to claim 1, it is characterised in that: the mass concentration of the hydrogen peroxide
It is 27.5%, 50% or 70%.
8. a kind of preparation method of epichlorohydrin according to claim 1, it is characterised in that: the detergent is by methanol, alkane
One or both of base phenol polyethenoxy ether composition.
9. a kind of preparation method of epichlorohydrin according to claim 1, it is characterised in that: the operating condition of the reaction
Are as follows: 30~110 DEG C of reaction temperature, reaction pressure normal pressure~3.0MPa, 10~60min of reaction time, catalyst detergent temperature
30~200 DEG C of degree, 2~72h of wash time.
10. a kind of preparation method of epichlorohydrin according to claim 1, it is characterised in that: the reactor is slurry bed system
Reactor, the paste state bed reactor are circulation flow reactor or the curing kettle with agitating device.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112299953A (en) * | 2020-11-27 | 2021-02-02 | 江苏扬农化工集团有限公司 | Method for treating catalyst regeneration liquid for preparing epichlorohydrin by hydrogen peroxide direct oxidation method |
| WO2022057931A1 (en) * | 2020-09-21 | 2022-03-24 | 江苏扬农化工集团有限公司 | Continuous synthesis process and continuous reaction device for epichlorohydrin |
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| US4833260A (en) * | 1982-07-28 | 1989-05-23 | Anic S.P.A. | Process for the epoxidation of olefinic compounds |
| US5888919A (en) * | 1996-11-25 | 1999-03-30 | Bartholic; David B. | Process for zeolitic catalyst reactivation |
| US20040260102A1 (en) * | 2003-06-18 | 2004-12-23 | Thomas Haas | Process for the epoxidation of propene |
| CN101486690A (en) * | 2009-02-24 | 2009-07-22 | 江苏扬农化工集团有限公司 | Production method of epoxy chloropropane by hydrogen peroxide method |
| CN101747297A (en) * | 2008-12-22 | 2010-06-23 | 中国石油化工股份有限公司 | Method for continuously producing epoxy chloropropane |
| CN101880263A (en) * | 2009-05-09 | 2010-11-10 | 中国石油化工集团公司 | Preparation method of epichlorohydrin |
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- 2019-09-02 CN CN201910823367.6A patent/CN110357835B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4833260A (en) * | 1982-07-28 | 1989-05-23 | Anic S.P.A. | Process for the epoxidation of olefinic compounds |
| US5888919A (en) * | 1996-11-25 | 1999-03-30 | Bartholic; David B. | Process for zeolitic catalyst reactivation |
| US20040260102A1 (en) * | 2003-06-18 | 2004-12-23 | Thomas Haas | Process for the epoxidation of propene |
| CN101747297A (en) * | 2008-12-22 | 2010-06-23 | 中国石油化工股份有限公司 | Method for continuously producing epoxy chloropropane |
| CN101486690A (en) * | 2009-02-24 | 2009-07-22 | 江苏扬农化工集团有限公司 | Production method of epoxy chloropropane by hydrogen peroxide method |
| CN101880263A (en) * | 2009-05-09 | 2010-11-10 | 中国石油化工集团公司 | Preparation method of epichlorohydrin |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022057931A1 (en) * | 2020-09-21 | 2022-03-24 | 江苏扬农化工集团有限公司 | Continuous synthesis process and continuous reaction device for epichlorohydrin |
| CN112299953A (en) * | 2020-11-27 | 2021-02-02 | 江苏扬农化工集团有限公司 | Method for treating catalyst regeneration liquid for preparing epichlorohydrin by hydrogen peroxide direct oxidation method |
| CN112299953B (en) * | 2020-11-27 | 2023-01-10 | 江苏扬农化工集团有限公司 | Method for treating catalyst regeneration liquid for preparing epichlorohydrin by hydrogen peroxide direct oxidation method |
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