CN110078684A - A kind of method that micro passage reaction is continuously synthesizing to epoxychloropropane - Google Patents
A kind of method that micro passage reaction is continuously synthesizing to epoxychloropropane Download PDFInfo
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- CN110078684A CN110078684A CN201910383853.0A CN201910383853A CN110078684A CN 110078684 A CN110078684 A CN 110078684A CN 201910383853 A CN201910383853 A CN 201910383853A CN 110078684 A CN110078684 A CN 110078684A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
- B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
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Abstract
The invention belongs to catalysis technical fields, are related to a kind of method for preparing epoxy resin key intermediate epoxychloropropane for catalysis, use micro passage reaction more particularly to a kind of, realize the continuous flow process of peroxide passivation epoxychloropropane.Micro passage reaction, using hydrogen peroxide as oxygen source, technique that a step epoxidation chloropropene serialization prepares epoxychloropropane are used the invention proposes a kind of.The technique is major advantage is that 1. the epoxidation time is foreshortened within 1 minute by a few houres, essentially eliminate epoxychloropropane in acid condition, the side reaction that hydrolysis generates glycerine monochlorohydrin occurs with water, epoxychloropropane yield and selectivity are high, reaction process is highly-safe, and " three wastes " amount is few；2. epoxidation reaction and product separation process have easy to operate, microcosmic mixing efficiency is effectively improved, prevents local excess temperature excessively high；3. the mass transfer of reaction, heat transfer property are enhanced, the advantages that hydrogen peroxide high conversion rate, safety greatly improves.
Description
Technical field
The invention belongs to catalysis technical fields, are related to one kind for catalysis and prepare epoxy resin key intermediate epoxy chloropropionate
The method of alkane uses micro passage reaction more particularly to a kind of, realizes the continuous flow process of peroxide passivation epoxychloropropane.
Background technique
Epoxychloropropane is a kind of very important chemical intermediate, be widely used in medicine, pesticide, coating, dyestuff and
The industries such as material are mainly used for synthetic glycerine, nitroglycerine, glass reinforced plastic, electrical isolation product, surfactant, sizing material, ion
The multiple products such as exchanger resin, plasticizer, chlorohydrin rubber and resin.The most important purposes of epoxychloropropane be used as epoxy group and
The raw materials such as phenoxy resin, high wet-strength resins and curing propylene-based rubber, 75% or more of total quantity consumed is for producing ring
Oxygen resin.
Industrialized epichlorohydrin production process mainly has propylene high-temperature chloridising, acetate propylene ester process and glycerol
Method.Mainly reaction process high temperature, by-product were more, feed stock conversion is low the shortcomings that propylene high-temperature chloridising, equipment seriously corroded,
Energy consumption height and sewage quantity are big；Acetate propylene ester process disadvantage be mainly reaction step mostly with expensive catalyst and cannot regenerate；Glycerol
The cleaning of method technique, is a kind of very competitive process route, but raw materials glycerine is the by-product of biodiesel, therefore glycerol
The manufacturing enterprise of method epoxychloropropane is often limited by the raw material supply of glycerol, can not expand production on a large scale.As country is sustainable
The propulsion of development strategy, it is therefore desirable to provide one kind, raw material sources are extensive, and the reaction time is short, high income, and green ring may be implemented
The technique of guarantor prepares epoxychloropropane.Currently, research both domestic and external is concentrated mainly on using hydrogen peroxide as oxygen source, the direct ring of chloropropene
Oxidation prepares the technique of epoxychloropropane, which does not generate brine waste, and only only the water of reaction generation, atom are sharp
With rate height, pollution is small, environmentally protective.
CN 101486690A provides one kind using modified Titanium Sieve Molecular Sieve as catalyst, and methanol is solvent, hydrogen peroxide
The method for preparing epoxychloropropane for oxidizing chloropropene；By chloropropene, methanol and titanium-silicon molecular sieve catalyst fine grained
It is put into reaction kettle, is warming up to 10-80 DEG C, be pumped into hydrogen peroxide and reacted；Grease is layered after reaction, and water phase is extracted through chloropropene
Afterwards directly with oily phase merging treatment, raffinate crystal evaporate recycle methanol, hydrogen peroxide conversion ratio >=99%, epoxychloropropane yield >=
95%.A large amount of methanol is introduced in reaction process and makees solvent, causes production procedure length, investment, energy consumption, operating cost high, by-product
Object especially can generate glycidol methyl ether in epoxidization reaction process and rectifying separation process, influence the product of epoxychloropropane
Quality.
CN103159703 B discloses a kind of method of chloropropene Direct Epoxidation continuous production epoxychloropropane, uses
Multi-stage stirring autoclave reactor, by chloropropene, aqueous hydrogen peroxide solution, catalyst (quaternary ammonium salt phosphor-tungstic heteropoly acid) slurry, or with
And solvent passes through the feed inlet of the reacted device lower part of metering pump respectively and is transported in reactor；25-95 DEG C of reaction temperature, reaction pressure
Power 0.1-1.0MPa, reaction solution can be homogeneous or heterogeneous state；The clear liquid with built-in filter is equipped on reactor top
Discharge port can isolate the clear liquid containing product, be provided with slurries below clear liquid discharge port, on the side wall of reactor middle and upper part
Bypass outlet, the complete material of the unreacted containing catalyst not filtered out is by mashing pump in reactor bottom end through slurry reflux entrance
Reflux is delivered in reactor, hydrogen peroxide conversion ratio >=99%, epoxychloropropane selectivity >=98%.Chloropropene in reaction process
Dosage substantially exceeds theoretical amount, and last handling process needs to recycle, and causes investment and operating cost high.
8729282 B2 of US describes a kind of by the catalysis oxidation of terminal olefin and hydrogen peroxide production 1,2- epoxidation
Aqueous solution 50mL (the complex catalyst containing manganese of catalyst is added into the four-hole boiling flask with stirring and thermometer for the method for object
0.0077g), sodium oxalate water solution 7.5mL (contain sodium oxalate 0.0151g), oxalic acid aqueous solution 7.5mL (containing sodium oxalate 0.0101g),
Water 10mL and chloropropene 11.4750g, is pumped into 35% hydrogen peroxide 19.4286g with the flow velocity of 8.8mL/h and carries out by 4 DEG C of reaction temperature
Reaction, hydrogen peroxide are pumped into Bi Jixu heat preservation 4h, hydrogen peroxide conversion ratio >=99%, epoxychloropropane selectivity >=95%.The technique
Reaction temperature is low, causes energy consumption and operating cost high；And wastewater flow rate is huge, about 8-10t/t epoxychloropropane；Hydrogen peroxide mistake
Amount, there are security risks.
Micro passage reaction is used the invention proposes a kind of, using hydrogen peroxide as oxygen source, a step epoxidation chloropropene is continuous
The technique that change prepares epoxychloropropane.The technique major advantage is that 1. the epoxidation time by a few houres foreshorten to 1 minute with
It is interior, it essentially eliminates epoxychloropropane in acid condition, the side reaction that hydrolysis generates glycerine monochlorohydrin, epoxy chlorine occurs with water
Propane recovering rate and selectivity are high, and reaction process is highly-safe, and " three wastes " amount is few；2. epoxidation reaction and product separation process have
It is easy to operate, microcosmic mixing efficiency is effectively improved, prevents local excess temperature excessively high；3. the mass transfer of reaction, heat transfer property are enhanced,
The advantages that hydrogen peroxide high conversion rate, safety greatly improves.
Summary of the invention
Simple the present invention is directed to overcome the deficiencies of the prior art and provide a kind of process flow, the reaction time is short, reaction efficiency
Height, strong operability is highly-safe, is easy to industrialized continuous synthesizing epoxy chloropropane process.The purpose of the present invention exists
In in micro passage reaction, chloropropene prepares epoxy by hydrogen peroxide epoxidation under water-soluble manganese complex catalyst action
Chloropropane realizes continuous production.
To achieve the above object, the technical solution adopted by the present invention carries out as steps described below:
The present invention relates to the synthetic method in the water-soluble manganese complex as oxidation catalyst is as follows:
In nitrogen atmosphere, Mn (ClO4) 26H2O 0.5g is added in ME3TACN (1g)/MA 30mL solution；?
The solution is stirred at room temperature after 1 hour, and sodium acetate 0.25g is added, stirs 2~3 days at 0 DEG C, vacuum freeze drying to precipitation
Pale blue is to clear crystal, as manganese complex catalyst.
(1) manganese complex catalyst aqueous solution configures: in 35 DEG C of conditions of water temperature after manganese complex catalyst and water are mixed
Lower sonic oscillation 0.5h, is completely dissolved catalyst, obtains catalyst aqueous solution；
(2) epoxidation reaction: catalyst aqueous solution is pumped into chloropropene to preheating plate preheating respectively and reaches estimated anti-
Answer temperature, it is preheated after mixed material enter reaction zone and contact, mix, react with hydrogen peroxide, after the completion of reaction process, from anti-
The efflux for answering area is epichlorohydrin reaction liquid；
(3) epoxychloropropane isolates and purifies and catalyst recycling: obtained reaction solution is cooled to rapidly 10 DEG C, it is quiet
1h is set, is layered, reaction oil reservoir simple distillation removes light component, then rectifying, can obtain the epoxychloropropane that purity is 99.9%；Instead
It answers water layer to recycle epoxychloropropane therein through negative pressure (- 0.095MPa) stripping, can be used for next catalysis after distillation water removal concentration
Reaction.
For the water-soluble manganese complex that may be used as oxidation catalyst, many suitable compounds are known.It urges
Agent typically comprises the manganese atom or multiple manganese atoms with one or more ligands；One or more of manganese are former
Son can be II, III or IV oxidation state, be activated during the reaction.
The concentration of catalyst aqueous solution of the present invention is 0.01-0.99g/L, preferably 0.10-0.50g/L.
The dosage of catalyst of the present invention is 0.01-0.99g/mol hydrogen peroxide, preferably 0.10-0.50g/mol dioxygen
Water；
Chloropropene of the present invention and hydrogen peroxide molar ratio are 2-4:1, preferably 2.5-3.5:1；
Hydrogen peroxide concentration of the present invention is 10-80%；It is preferred that 30-70%
Reaction temperature of the present invention is 10-80 DEG C, preferably 30-60 DEG C；
Material of the present invention is 1-10min in the residence time of reaction zone, and the preferably residence time is 2-5min.
Specific embodiment
Embodiment 1
(1) after manganese complex catalyst and water being mixed under the conditions of 35 DEG C of water temperature sonic oscillation 0.5h, keep catalyst complete
Fully dissolved, concentration are the catalyst aqueous solution of 0.30g/L.
(2) hydrogen peroxide concentration is 80%, and according to material chloropropene and hydrogen peroxide molar ratio 2:1, catalyst amount is
Two strands of materials of ratio of 0.10g/mol hydrogen peroxide are pumped into preheating plate preheating respectively and reach estimated 30 DEG C of reaction temperature；Through pre-
Mixed material after heat enters reaction zone and contacts, mixes, reacts with hydrogen peroxide, wherein control epoxidation stage temperature is 30 DEG C；
Reaction controlling material flow, residence time 2min；After the completion of reaction process, the efflux for leaving reaction zone is epoxychloropropane
Reaction solution；Epichlorohydrin reaction liquid is analyzed, the conversion ratio of hydrogen peroxide is 98.5%, the yield and selectivity point of epoxychloropropane
It Wei 95.5% and 98.6%.
Embodiment 2
(1) after manganese complex catalyst and water being mixed under the conditions of 35 DEG C of water temperature sonic oscillation 0.5h, keep catalyst complete
Fully dissolved, concentration are the catalyst aqueous solution of 0.10g/L.
(2) hydrogen peroxide concentration is 30%, and according to material chloropropene and hydrogen peroxide molar ratio 2.5:1, catalyst amount is
Two strands of materials of ratio of 0.50g/mol hydrogen peroxide are pumped into preheating plate preheating respectively and reach estimated 60 DEG C of reaction temperature；Through pre-
Mixed material after heat enters reaction zone and contacts, mixes, reacts with hydrogen peroxide, wherein control epoxidation stage temperature is 60 DEG C；
Reaction controlling material flow, residence time 3min；After the completion of reaction process, the efflux for leaving reaction zone is epoxychloropropane
Reaction solution；Epichlorohydrin reaction liquid is analyzed, the conversion ratio of hydrogen peroxide is 100%, the yield and selectivity point of epoxychloropropane
It Wei 98.8% and 99.1%.
Embodiment 3
(1) after manganese complex catalyst and water being mixed under the conditions of 35 DEG C of water temperature sonic oscillation 0.5h, keep catalyst complete
Fully dissolved, concentration are the catalyst aqueous solution of 0.01g/L.
(2) hydrogen peroxide concentration is 70%, and according to material chloropropene and hydrogen peroxide molar ratio 3:1, catalyst amount is
Two strands of materials of ratio of 0.01g/mol hydrogen peroxide are pumped into preheating plate preheating respectively and reach estimated 80 DEG C of reaction temperature；Through pre-
Mixed material after heat enters reaction zone and contacts, mixes, reacts with hydrogen peroxide, wherein control epoxidation stage temperature is 80 DEG C；
Reaction controlling material flow, residence time 5min；After the completion of reaction process, the efflux for leaving reaction zone is epoxychloropropane
Reaction solution；Epichlorohydrin reaction liquid is analyzed, the conversion ratio of hydrogen peroxide is 100%, the yield and selectivity point of epoxychloropropane
It Wei 90.3% and 98.2%.
Embodiment 4
(1) after manganese complex catalyst and water being mixed under the conditions of 35 DEG C of water temperature sonic oscillation 0.5h, keep catalyst complete
Fully dissolved, concentration are the catalyst aqueous solution of 0.99g/L.
(2) hydrogen peroxide concentration is 10%, and according to material chloropropene and hydrogen peroxide molar ratio 3.5:1, catalyst amount is
Two strands of materials of ratio of 0.99g/mol hydrogen peroxide are pumped into preheating plate preheating respectively and reach estimated 10 DEG C of reaction temperature；Through pre-
Mixed material after heat enters reaction zone and contacts, mixes, reacts with hydrogen peroxide, wherein control epoxidation stage temperature is 10 DEG C；
Reaction controlling material flow, residence time 10min；After the completion of reaction process, the efflux for leaving reaction zone is epoxy chloropropionate
Alkane reaction solution；Epichlorohydrin reaction liquid is analyzed, the conversion ratio of hydrogen peroxide is 92.9%, the yield and selectivity of epoxychloropropane
Respectively 92.1% and 99.9%.
Embodiment 5
(1) after manganese complex catalyst and water being mixed under the conditions of 35 DEG C of water temperature sonic oscillation 0.5h, keep catalyst complete
Fully dissolved, concentration are the catalyst aqueous solution of 0.50g/L.
(2) hydrogen peroxide concentration is 50%, and according to material chloropropene and hydrogen peroxide molar ratio 4:1, catalyst amount is
Two strands of materials of ratio of 0.30g/mol hydrogen peroxide are pumped into preheating plate preheating respectively and reach estimated 40 DEG C of reaction temperature；Through pre-
Mixed material after heat enters reaction zone and contacts, mixes, reacts with hydrogen peroxide, wherein control epoxidation stage temperature is 40 DEG C；
Reaction controlling material flow, residence time 1min；After the completion of reaction process, the efflux for leaving reaction zone is epoxychloropropane
Reaction solution；Epichlorohydrin reaction liquid is analyzed, the conversion ratio of hydrogen peroxide is 100%, the yield and selectivity point of epoxychloropropane
It Wei 98.9% and 99.9%.
Comparative example 1
The complex catalyst aqueous solution 100mL of chloropropene 52.0g and 0.50g/L, heating are put into 500mL four-hole boiling flask
40 DEG C, 50% hydrogen peroxide 11.5g is added dropwise in 10min under stirring, reacts 50min at 0 DEG C；Epoxy is analyzed after reaction
Chloropropane reaction solution, the conversion ratio of hydrogen peroxide are 78.4%, and the yield and selectivity of epoxychloropropane are respectively 76.9% He
98.4%.
Comparative example 2
The complex catalyst aqueous solution 500mL that chloropropene 22.95g and 0.10g/L are put into 500mL four-hole boiling flask, rises
30% hydrogen peroxide 11.3g is added dropwise under stirring, reacts 5min at 30 DEG C for 30 DEG C of temperature in 5min；Ring is analyzed after reaction
Oxygen chloropropane reaction solution, the conversion ratio of hydrogen peroxide are 98.1%, and the yield and selectivity of epoxychloropropane are respectively 55.6% He
56.8%.
Comparative example 3
The phosphotungstic acid catalyst that chloropropene 314g and 25g are put into 500mL four-hole boiling flask, is warming up to reflux, is stirring
30% hydrogen peroxide 113.3g is added dropwise under state in 2h, reacts 180min at 42-48 DEG C；Analysis epoxychloropropane is anti-after reaction
Liquid is answered, the conversion ratio of hydrogen peroxide is 99.1%, and the yield and selectivity of epoxychloropropane are respectively 90.6% and 95.3%.
Comparative example 4
Chloropropene 157g, 150g methanol and titanium-silicon molecular sieve catalyst are put into 500mL four-hole boiling flask, are warming up to back
30% hydrogen peroxide 113.3g is added dropwise under stirring, reacts 60min at 40-45 DEG C for stream in 1h；Epoxy is analyzed after reaction
Chloropropane reaction solution, the conversion ratio of hydrogen peroxide are 98.5%, and the yield and selectivity of epoxychloropropane are respectively 93.6% He
95.3%.
Embodiment 6
(1) after manganese complex catalyst and water being mixed under the conditions of 35 DEG C of water temperature sonic oscillation 0.5h, keep catalyst complete
Fully dissolved, concentration are the catalyst aqueous solution of 0.50g/L.
(2) hydrogen peroxide concentration is 50%, and according to material chloropropene and hydrogen peroxide molar ratio 4:1, catalyst amount is
Two strands of materials of ratio of 0.30g/mol hydrogen peroxide are pumped into preheating plate preheating respectively and reach estimated 40 DEG C of reaction temperature；Through pre-
Mixed material after heat enters reaction zone and contacts, mixes, reacts with hydrogen peroxide, wherein control epoxidation stage temperature is 40 DEG C；
Reaction controlling material flow, residence time 1min；After the completion of reaction process, the efflux for leaving reaction zone is epoxychloropropane
Reaction solution；Epichlorohydrin reaction liquid is analyzed, the conversion ratio of hydrogen peroxide is 100%, the yield and selectivity point of epoxychloropropane
It Wei 98.9% and 99.9%.
(3) obtained reaction solution is placed into 10 DEG C of cooling 2h, layering, reaction oil reservoir simple distillation removes a small amount of light component,
Rectifying again can obtain the epoxychloropropane that purity is 99.9%；It is therein through the recycling of negative pressure (- 0.095MPa) stripping to react water layer
Epoxychloropropane, distillation water removal are concentrated into 0.50g/L containing catalyst, and for catalysis reaction next time, carrying out next batch circulation makes
With recycling 5 times altogether.
1 embodiment of table, 6 catalyst circulation reactivity worth data
| Catalyst circulation number | Hydrogen peroxide conversion ratio/% | Epoxychloropropane yield/% | Epoxychloropropane selectivity/% |
| 1 | 100 | 98.9 | 99.9 |
| 2 | 99.3 | 97.6 | 99.9 |
| 3 | 99.3 | 98.6 | 99.9 |
| 4 | 99.1 | 98.4 | 99.5 |
| 5 | 98.9 | 98.6 | 99.5 |
Content of the present invention is not limited in embodiment content of the present invention.
Specific case used herein is expounded structure of the invention and embodiment, the explanation of above embodiments
It is merely used to help understand the core idea of the present invention.It should be pointed out that for those skilled in the art,
Without departing from the principles of the invention, can be with several improvements and modifications are made to the present invention, these improvement and modification are also fallen
Enter in the protection scope of the claims in the present invention.
Claims (9)
1. a kind of method that a step epoxidation chloropropene serialization prepares epoxychloropropane, which comprises the following steps:
(1) manganese complex catalyst aqueous solution configures: surpassing under the conditions of 35 DEG C of water temperature after manganese complex catalyst and water are mixed
Sound oscillation 0.5h, is completely dissolved catalyst, obtains catalyst aqueous solution；
(2) epoxidation reaction: catalyst aqueous solution is pumped into chloropropene to preheating plate preheating respectively reaches estimated and react temperature
Degree, it is preheated after mixed material enter reaction zone and contact, mix, react with hydrogen peroxide, after the completion of reaction process, from reaction zone
Efflux be epichlorohydrin reaction liquid；
(3) epoxychloropropane isolates and purifies and catalyst recycling: obtained reaction solution being cooled to rapidly 10 DEG C, is stood
1h, layering, reaction oil reservoir simple distillation remove light component, then rectifying, can obtain the epoxychloropropane that purity is 99.9%；Reaction
Water layer recycles epoxychloropropane therein through negative pressure (- 0.095MPa) stripping, and it is anti-to can be used for catalysis next time after distillation water removal concentration
It answers.
2. the method that step epoxidation chloropropene serialization according to claim 1 prepares epoxychloropropane, feature exist
In manganese complex catalyst typically comprises the manganese atom or multiple manganese atoms with one or more ligands；It is described
One or more manganese atoms can be II, III or IV oxidation state, be activated during the reaction.
3. the method that step epoxidation chloropropene serialization according to claim 1 prepares epoxychloropropane, feature exist
In the concentration of catalyst aqueous solution is 0.01-0.99g/L, preferably 0.10-0.50g/L in step 1.
4. the method that step epoxidation chloropropene serialization according to claim 1 prepares epoxychloropropane, feature exist
In the dosage of catalyst is 0.01-0.99g/mol hydrogen peroxide, preferably 0.10-0.50g/mol hydrogen peroxide in step 2.
5. the method that step epoxidation chloropropene serialization according to claim 1 prepares epoxychloropropane, feature exist
In chloropropene and hydrogen peroxide molar ratio are 2-4:1, preferably 2.5-3.5:1 in step 2.
6. the method that step epoxidation chloropropene serialization according to claim 1 prepares epoxychloropropane, feature exist
In hydrogen peroxide concentration is 10-80wt% in step 2；It is preferred that 30-70wt%.
7. the method that step epoxidation chloropropene serialization according to claim 1 prepares epoxychloropropane, feature exist
In reaction temperature is 10-80 DEG C, preferably 30-60 DEG C in step 2.
8. the method that step epoxidation chloropropene serialization according to claim 1 prepares epoxychloropropane, feature exist
In material is 1-10min in the residence time of reaction zone in step 2, and the preferably residence time is 2-5min.
9. the method that step epoxidation chloropropene serialization according to claim 1 prepares epoxychloropropane, feature exist
In the synthetic method of manganese complex catalyst is as follows:
In nitrogen atmosphere, Mn (ClO4) 26H2O0.5g is added in ME3TACN (1g)/MA30mL solution；At room temperature
The solution is stirred after 1 hour, sodium acetate 0.25g is added, is stirred 2~3 days at 0 DEG C, vacuum freeze drying to precipitation pale blue is extremely
Clear crystal, as manganese complex catalyst.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110575809A (en) * | 2019-09-27 | 2019-12-17 | 江苏扬农化工集团有限公司 | Reactor and method for continuously synthesizing epoxy chloropropane |
| CN113999190A (en) * | 2021-11-19 | 2022-02-01 | 江苏瑞祥化工有限公司 | Method for decoloring microchannel continuous flow epichlorohydrin and hydrogen peroxide |
| CN115385873A (en) * | 2022-10-25 | 2022-11-25 | 山东华夏神舟新材料有限公司 | Continuous synthesis method of perfluoro-2, 3-epoxy-2-methylpentane |
| CN116239764A (en) * | 2022-12-13 | 2023-06-09 | 山东联欣环保科技有限公司 | Continuous production process of carbon dioxide-based biodegradable polymer |
| CN116514741A (en) * | 2023-07-04 | 2023-08-01 | 山东民基新材料科技有限公司 | Process for producing epoxy chloropropane by utilizing micro-interface reaction |
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| CN115385873A (en) * | 2022-10-25 | 2022-11-25 | 山东华夏神舟新材料有限公司 | Continuous synthesis method of perfluoro-2, 3-epoxy-2-methylpentane |
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| CN116514741A (en) * | 2023-07-04 | 2023-08-01 | 山东民基新材料科技有限公司 | Process for producing epoxy chloropropane by utilizing micro-interface reaction |
| CN116514741B (en) * | 2023-07-04 | 2023-09-26 | 山东民基新材料科技有限公司 | Process for producing epoxy chloropropane by utilizing micro-interface reaction |
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