CN110078684B - Method for continuously synthesizing epichlorohydrin by using microchannel reactor - Google Patents
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- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
Abstract
The invention belongs to the technical field of catalysis, relates to a method for preparing epoxy resin key intermediate epichlorohydrin by catalysis, and particularly relates to a continuous flow process for realizing epichlorohydrin by a hydrogen peroxide method by using a microchannel reactor. The invention provides a process for continuously preparing epichlorohydrin by one-step epoxidation of chloropropene by adopting a microchannel reactor and using hydrogen peroxide as an oxygen source. The process has the main advantages that: the epoxidation time is shortened from several hours to within 1 minute, the side reaction that epichlorohydrin is hydrolyzed with water to generate monochloropropanediol under the acidic condition is basically eliminated, the yield and the selectivity of the epichlorohydrin are high, the safety of the reaction process is high, and the amount of three wastes is small; the epoxidation reaction and the product separation process are simple to operate, the micromixing efficiency is effectively improved, and the local over-temperature is prevented from being too high; thirdly, the mass transfer and heat transfer performance of the reaction is enhanced, the conversion rate of the hydrogen peroxide is high, the safety is greatly improved, and the like.
Description
Technical Field
The invention belongs to the technical field of catalysis, relates to a method for preparing epoxy resin key intermediate epichlorohydrin by catalysis, and particularly relates to a continuous flow process for realizing epichlorohydrin by a hydrogen peroxide method by using a microchannel reactor.
Background
Epichlorohydrin is a very important chemical intermediate, is widely applied to industries such as medicines, pesticides, coatings, dyes and materials, and is mainly used for synthesizing glycerol, nitroglycerin explosive, glass fiber reinforced plastics, electrical insulators, surfactants, sizing materials, ion exchange resins, plasticizers, epichlorohydrin rubber, resins and other products. The epichlorohydrin is mainly used as raw materials of epoxy and phenoxy resins, high-wet-strength resins, cured propylene-based rubbers and the like, and more than 75% of the total consumption amount of the epichlorohydrin is used for producing epoxy resins.
The industrialized production process of epichlorohydrin mainly comprises a propylene high-temperature chlorination method, an acetate propylene ester method and a glycerol method. The disadvantages of the propylene high-temperature chlorination method are mainly high temperature in the reaction process, more byproducts, low raw material conversion rate, serious equipment corrosion, high energy consumption and large sewage amount; the defects of the acetate propylene ester method are mainly that the reaction steps are multiple, the catalyst is expensive and the catalyst cannot be regenerated; the glycerol method is clean in process and is a very competitive process route, but the raw material glycerol is a byproduct of biodiesel, so that enterprises producing epichlorohydrin by the glycerol method are often limited by the raw material supply of glycerol and cannot expand the production on a large scale. With the advancement of the national sustainable development strategy, the method needs to provide a method which has the advantages of wide raw material source, short reaction time and high yield and can realize the green and environment-friendly process for preparing the epichlorohydrin. At present, the research at home and abroad mainly focuses on the process for preparing epoxy chloropropane by directly epoxidizing chloropropene by using hydrogen peroxide as an oxygen source, and the process route does not generate salt-containing wastewater, only generates water generated by reaction, and has the advantages of high atom utilization rate, small pollution and environmental protection.
CN 101486690A provides a method for preparing epichlorohydrin by using a modified titanium silicalite molecular sieve as a catalyst, methanol as a solvent and hydrogen peroxide as an oxidant to oxidize chloropropene; placing chloropropene, methanol and titanium silicalite molecular sieve catalyst fine particles into a reaction kettle, heating to 10-80 ℃, and pumping hydrogen peroxide for reaction; and (3) oil and water are separated after reaction, the water phase is extracted by chloropropene and then is directly combined with the oil phase for treatment, the extraction residual water is rectified to recover methanol, the conversion rate of hydrogen peroxide is more than or equal to 99 percent, and the yield of epoxy chloropropane is more than or equal to 95 percent. A large amount of methanol is introduced as a solvent in the reaction process, so that the production process is long, the investment, the energy consumption and the operation cost are high, and the by-products can generate glycidyl methyl ether particularly in the epoxidation reaction process and the rectification separation process, so that the product quality of epoxy chloropropane is influenced.
CN 103159703B discloses a method for continuously producing epichlorohydrin by direct epoxidation of chloropropene, which comprises adopting a multi-stage stirred tank reactor to convey chloropropene, aqueous hydrogen peroxide, catalyst (quaternary ammonium phosphotungstate) slurry or solvent into the reactor through a metering pump via a feed inlet at the lower part of the reactor; the reaction temperature is 25-95 ℃, the reaction pressure is 0.1-1.0MPa, and the reaction solution can be in a homogeneous phase or heterogeneous phase state; the upper part of the reactor is provided with a clear liquid discharge port with a built-in filter, clear liquid containing products can be separated, a slurry backflow outlet is arranged below the clear liquid discharge port and on the side wall of the middle upper part of the reactor, unreacted materials containing catalysts which are not filtered out are conveyed to the reactor through a slurry backflow inlet at the bottom end of the reactor in a backflow mode through a slurry pump, the conversion rate of hydrogen peroxide is more than or equal to 99%, and the selectivity of epoxy chloropropane is more than or equal to 98%. The consumption of chloropropene in the reaction process greatly exceeds the theoretical amount, and the post-treatment process needs to be recovered, so that the investment and operation cost is high.
US 8729282B 2 describes a method for producing 1, 2-epoxide by catalytic oxidation of terminal olefin and hydrogen peroxide, 50mL of aqueous solution of catalyst (containing 0.0077g of manganese complex catalyst), 7.5mL of aqueous solution of sodium oxalate (containing 0.0151g of sodium oxalate), 7.5mL of aqueous solution of oxalic acid (containing 0.0101g of sodium oxalate), 10mL of water and 11.4750g of chloropropene are added into a four-neck flask with a stirrer and a thermometer, the reaction temperature is 4 ℃, 35% hydrogen peroxide solution 19.4286g is pumped at the flow rate of 8.8mL/h for reaction, the temperature is kept for 4h after the hydrogen peroxide solution is pumped, the conversion rate of the hydrogen peroxide solution is more than or equal to 99%, and the selectivity of the epoxy chloropropane is more than or equal to 95%. The reaction temperature of the process is low, so that the energy consumption and the operation cost are high; the waste water amount is large and is about 8-10t/t of epoxy chloropropane; the hydrogen peroxide is excessive, so that potential safety hazards exist.
The invention provides a process for continuously preparing epichlorohydrin by one-step epoxidation of chloropropene by adopting a microchannel reactor and using hydrogen peroxide as an oxygen source. The process has the main advantages that: the epoxidation time is shortened from several hours to within 1 minute, the side reaction that epichlorohydrin is hydrolyzed with water to generate monochloropropanediol under the acidic condition is basically eliminated, the yield and the selectivity of the epichlorohydrin are high, the safety of the reaction process is high, and the amount of three wastes is small; the epoxidation reaction and the product separation process are simple to operate, the micromixing efficiency is effectively improved, and the local over-temperature is prevented from being too high; thirdly, the mass transfer and heat transfer performance of the reaction is enhanced, the conversion rate of the hydrogen peroxide is high, the safety is greatly improved, and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the process method for continuously synthesizing the epichlorohydrin, which has the advantages of simple process flow, short reaction time, high reaction efficiency, strong operability, high safety and easiness in industrialization. The invention aims to prepare epichlorohydrin by epoxidizing chloropropene with hydrogen peroxide under the action of a water-soluble manganese complex catalyst in a microchannel reactor, thereby realizing continuous production.
In order to achieve the purpose, the technical scheme adopted by the invention is carried out according to the following steps:
the invention relates to a method for synthesizing a water-soluble manganese complex used as an oxidation catalyst, which comprises the following steps:
under nitrogen atmosphere, 0.5g of Mn (ClO4) 2.6H 2O 0.5 was added to a solution of ME3TACN (1g)/MA 30 mL; and stirring the solution at room temperature for 1 hour, adding 0.25g of sodium acetate, stirring at 0 ℃ for 2-3 days, and carrying out vacuum freeze drying until light blue is separated out to obtain colorless crystals, namely the manganese complex catalyst.
(1) Preparation of manganese complex catalyst aqueous solution: mixing a manganese complex catalyst with water, and then carrying out ultrasonic oscillation for 0.5h at the water temperature of 35 ℃ to completely dissolve the catalyst to obtain a catalyst aqueous solution;
(2) epoxidation reaction: respectively pumping the catalyst aqueous solution and chloropropene into a preheating plate to preheat to reach an expected reaction temperature, allowing the preheated mixed material to enter a reaction zone to contact with hydrogen peroxide, mixing and reacting, and obtaining an effluent liquid from the reaction zone, namely an epichlorohydrin reaction liquid after the reaction process is finished;
(3) separation and purification of epoxy chloropropane and cyclic utilization of catalyst: quickly cooling the obtained reaction liquid to 10 ℃, standing for 1h, layering, simply distilling a reaction oil layer to remove light components, and rectifying to obtain epoxy chloropropane with the purity of 99.9%; the reaction water layer is stripped under negative pressure (-0.095MPa) to recover epichlorohydrin, and the epichlorohydrin is distilled to remove water and concentrated to be used for next catalytic reaction.
Many suitable complexes are known for water soluble manganese complexes that can be used as oxidation catalysts. The catalyst typically comprises a manganese atom or atoms coordinated to one or more ligands; the one or more manganese atoms may be in oxidation state II, III or IV and are activated during the reaction.
The concentration of the aqueous catalyst solution of the present invention is 0.01 to 0.99g/L, preferably 0.10 to 0.50 g/L.
The dosage of the catalyst is 0.01-0.99g/mol of hydrogen peroxide, preferably 0.10-0.50g/mol of hydrogen peroxide;
the mol ratio of chloropropene to hydrogen peroxide is 2-4:1, preferably 2.5-3.5: 1;
the concentration of the hydrogen peroxide is 10-80%; preferably 30-70%
The reaction temperature is 10-80 ℃, preferably 30-60 ℃;
the residence time of the materials in the reaction zone is 1-10min, and the preferred residence time is 2-5 min.
Detailed Description
Example 1
(1) Mixing the manganese complex catalyst with water, and ultrasonically oscillating at 35 deg.C for 0.5h to completely dissolve the catalyst, wherein the concentration of the catalyst is 0.30 g/L.
(2) The concentration of hydrogen peroxide is 80%, and two materials are respectively pumped into a preheating plate to be preheated to reach the predicted reaction temperature of 30 ℃ according to the proportion that the mol ratio of chloropropene to hydrogen peroxide is 2:1 and the dosage of the catalyst is 0.10g/mol of hydrogen peroxide; the preheated mixed material enters a reaction zone to contact, mix and react with hydrogen peroxide, wherein the temperature of an epoxidation stage is controlled to be 30 ℃; controlling the flow rate of the materials by reaction, and keeping the reaction time for 2 min; after the reaction process is finished, effluent liquid leaving the reaction zone is epoxy chloropropane reaction liquid; when the epichlorohydrin reaction liquid is analyzed, the conversion rate of the hydrogen peroxide is 98.5%, and the yield and the selectivity of the epichlorohydrin are 95.5% and 98.6% respectively.
Example 2
(1) Mixing the manganese complex catalyst with water, and ultrasonically oscillating at 35 deg.C for 0.5h to completely dissolve the catalyst, wherein the concentration of the catalyst is 0.10 g/L.
(2) The concentration of hydrogen peroxide is 30 percent, and two materials are respectively pumped into a preheating plate to be preheated to reach the predicted reaction temperature of 60 ℃ according to the proportion that the mol ratio of chloropropene to hydrogen peroxide is 2.5:1 and the dosage of the catalyst is 0.50 g/mol; the preheated mixed material enters a reaction zone to contact, mix and react with hydrogen peroxide, wherein the temperature of an epoxidation stage is controlled to be 60 ℃; controlling the flow rate of the materials by reaction, and keeping the reaction time for 3 min; after the reaction process is finished, effluent liquid leaving the reaction zone is epoxy chloropropane reaction liquid; when the epichlorohydrin reaction liquid is analyzed, the conversion rate of the hydrogen peroxide is 100 percent, and the yield and the selectivity of the epichlorohydrin are respectively 98.8 percent and 99.1 percent.
Example 3
(1) Mixing the manganese complex catalyst with water, and ultrasonically oscillating at 35 deg.C for 0.5h to completely dissolve the catalyst, wherein the concentration of the catalyst is 0.01 g/L.
(2) The concentration of hydrogen peroxide is 70 percent, and two materials are respectively pumped into a preheating plate to preheat to reach the predicted reaction temperature of 80 ℃ according to the proportion that the mol ratio of chloropropene to hydrogen peroxide is 3:1 and the dosage of the catalyst is 0.01g/mol of hydrogen peroxide; the preheated mixed material enters a reaction zone to contact, mix and react with hydrogen peroxide, wherein the temperature of an epoxidation stage is controlled to be 80 ℃; controlling the flow rate of the materials by reaction, and keeping the reaction time for 5 min; after the reaction process is finished, effluent liquid leaving the reaction zone is epoxy chloropropane reaction liquid; when the epichlorohydrin reaction liquid is analyzed, the conversion rate of the hydrogen peroxide is 100 percent, and the yield and the selectivity of the epichlorohydrin are respectively 90.3 percent and 98.2 percent.
Example 4
(1) Mixing the manganese complex catalyst with water, and ultrasonically oscillating at 35 deg.C for 0.5h to completely dissolve the catalyst, wherein the concentration of the catalyst is 0.99 g/L.
(2) The concentration of hydrogen peroxide is 10 percent, and two materials are respectively pumped into a preheating plate to be preheated to reach the predicted reaction temperature of 10 ℃ according to the proportion that the mol ratio of chloropropene to hydrogen peroxide is 3.5:1 and the dosage of the catalyst is 0.99 g/mol; the preheated mixed material enters a reaction zone to be contacted, mixed and reacted with hydrogen peroxide, wherein the temperature of an epoxidation stage is controlled to be 10 ℃; controlling the flow rate of the materials by reaction, and keeping the reaction time for 10 min; after the reaction process is finished, effluent liquid leaving the reaction zone is epoxy chloropropane reaction liquid; when the epichlorohydrin reaction liquid is analyzed, the conversion rate of the hydrogen peroxide is 92.9%, and the yield and the selectivity of the epichlorohydrin are respectively 92.1% and 99.9%.
Example 5
(1) Mixing the manganese complex catalyst with water, and ultrasonically oscillating at 35 deg.C for 0.5h to completely dissolve the catalyst, wherein the concentration of the catalyst is 0.50 g/L.
(2) The concentration of hydrogen peroxide is 50 percent, and two materials are respectively pumped into a preheating plate to be preheated to reach the predicted reaction temperature of 40 ℃ according to the proportion that the mol ratio of chloropropene to hydrogen peroxide is 4:1 and the dosage of the catalyst is 0.30 g/mol; the preheated mixed material enters a reaction zone to contact, mix and react with hydrogen peroxide, wherein the temperature of an epoxidation stage is controlled to be 40 ℃; controlling the flow rate of the materials by reaction, and keeping the reaction time for 1 min; after the reaction process is finished, effluent liquid leaving the reaction zone is epoxy chloropropane reaction liquid; when the epichlorohydrin reaction liquid is analyzed, the conversion rate of the hydrogen peroxide is 100 percent, and the yield and the selectivity of the epichlorohydrin are respectively 98.9 percent and 99.9 percent.
Comparative example 1
Adding 52.0g of chloropropene and 100mL of 0.50g/L complex catalyst aqueous solution into a 500mL four-neck flask, heating to 40 ℃, dropwise adding 11.5g of 50% hydrogen peroxide within 10min under a stirring state, and reacting for 50min at 0 ℃; after the reaction is finished, the reaction liquid of the epoxy chloropropane is analyzed, the conversion rate of the hydrogen peroxide is 78.4 percent, and the yield and the selectivity of the epoxy chloropropane are respectively 76.9 percent and 98.4 percent.
Comparative example 2
Adding 22.95g of chloropropene and 500mL of 0.10g/L complex catalyst aqueous solution into a 500mL four-neck flask, heating to 30 ℃, dropwise adding 11.3g of 30% hydrogen peroxide within 5min under a stirring state, and reacting for 5min at 30 ℃; after the reaction is finished, the reaction liquid of the epoxy chloropropane is analyzed, the conversion rate of the hydrogen peroxide is 98.1 percent, and the yield and the selectivity of the epoxy chloropropane are respectively 55.6 percent and 56.8 percent.
Comparative example 3
Putting 314g of chloropropene and 25g of phosphotungstic acid catalyst into a 500mL four-neck flask, heating to reflux, dropwise adding 113.3g of 30% hydrogen peroxide within 2h under a stirring state, and reacting for 180min at 42-48 ℃; after the reaction is finished, the reaction liquid of the epoxy chloropropane is analyzed, the conversion rate of the hydrogen peroxide is 99.1 percent, and the yield and the selectivity of the epoxy chloropropane are respectively 90.6 percent and 95.3 percent.
Comparative example 4
Adding 157g of chloropropene, 150g of methanol and a titanium silicalite molecular sieve catalyst into a 500mL four-neck flask, heating to reflux, dropwise adding 113.3g of 30% hydrogen peroxide within 1h under a stirring state, and reacting for 60min at 40-45 ℃; after the reaction is finished, the reaction liquid of the epoxy chloropropane is analyzed, the conversion rate of the hydrogen peroxide is 98.5 percent, and the yield and the selectivity of the epoxy chloropropane are 93.6 percent and 95.3 percent respectively.
Example 6
(1) Mixing the manganese complex catalyst with water, and ultrasonically oscillating at 35 deg.C for 0.5h to completely dissolve the catalyst, wherein the concentration of the catalyst is 0.50 g/L.
(2) The concentration of hydrogen peroxide is 50 percent, and two materials are respectively pumped into a preheating plate to be preheated to reach the predicted reaction temperature of 40 ℃ according to the proportion that the mol ratio of chloropropene to hydrogen peroxide is 4:1 and the dosage of the catalyst is 0.30 g/mol; the preheated mixed material enters a reaction zone to contact, mix and react with hydrogen peroxide, wherein the temperature of an epoxidation stage is controlled to be 40 ℃; controlling the flow rate of the materials by reaction, and keeping the reaction time for 1 min; after the reaction process is finished, effluent liquid leaving the reaction zone is epoxy chloropropane reaction liquid; when the epichlorohydrin reaction liquid is analyzed, the conversion rate of the hydrogen peroxide is 100 percent, and the yield and the selectivity of the epichlorohydrin are respectively 98.9 percent and 99.9 percent.
(3) Placing the obtained reaction liquid at 10 ℃ for cooling for 2h, layering, simply distilling a reaction oil layer to remove a small amount of light components, and rectifying to obtain epoxy chloropropane with the purity of 99.9%; and (3) stripping the reaction water layer under negative pressure (-0.095MPa) to recover epoxy chloropropane, removing water by distillation, concentrating to 0.50g/L of catalyst, and recycling for 5 times.
Table 1 example 6 catalyst cycle reaction performance data
| Number of catalyst cycles | Hydrogen peroxide conversion/%) | Yield of epichlorohydrin/% | Epichlorohydrin 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 |
The invention is not limited to the embodiments of the invention described.
The structure and the implementation of the present invention are described herein by using specific examples, and the above description of the examples is only used to help understand the core idea of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (14)
1. The method for continuously preparing epichlorohydrin by one-step epoxidation of chloropropene is characterized by comprising the following steps:
(1) preparation of manganese complex catalyst aqueous solution: mixing a manganese complex catalyst with water, and then carrying out ultrasonic oscillation for 0.5h at the water temperature of 35 ℃ to completely dissolve the catalyst to obtain a catalyst aqueous solution;
(2) epoxidation reaction: respectively pumping the catalyst aqueous solution and chloropropene into a preheating plate to preheat to reach an expected reaction temperature, allowing the preheated mixed material to enter a reaction zone to contact with hydrogen peroxide, mixing and reacting, and obtaining an effluent liquid from the reaction zone, namely an epichlorohydrin reaction liquid after the reaction process is finished;
(3) separation and purification of epoxy chloropropane and cyclic utilization of catalyst: quickly cooling the obtained reaction liquid to 10 ℃, standing for 1h, layering, simply distilling a reaction oil layer to remove light components, and rectifying to obtain epoxy chloropropane with the purity of 99.9%; the reaction water layer is stripped under negative pressure of-0.095 MPa to recover epoxy chloropropane, and the reaction water layer can be used for the next catalytic reaction after being distilled, dewatered and concentrated, and the synthesis method of the manganese complex catalyst comprises the following steps:
mn (ClO) in a nitrogen atmosphere4)2·6H2Adding 0.5g of O into a solution of ME3TACN 1g/MA 30 mL; and stirring the solution at room temperature for 1 hour, adding 0.25g of sodium acetate, stirring at 0 ℃ for 2-3 days, and carrying out vacuum freeze drying until light blue is separated out to obtain colorless crystals, namely the manganese complex catalyst.
2. The process for the continuous preparation of epichlorohydrin by one-step epoxidation of chloropropene according to claim 1, characterized in that the manganese complex catalyst typically comprises a manganese atom or a plurality of manganese atoms coordinated with one or more ligands; the one or more manganese atoms may be in oxidation state II, III or IV and are activated during the reaction.
3. The process for the continuous preparation of epichlorohydrin by one-step epoxidation of chloropropene according to claim 1, wherein the concentration of the catalyst aqueous solution in step 1 is 0.01-0.99 g/L.
4. The process for the continuous preparation of epichlorohydrin by one-step epoxidation of chloropropene according to claim 3, wherein the concentration of the catalyst aqueous solution in step 1 is 0.10-0.50 g/L.
5. The method for continuously preparing epichlorohydrin by one-step epoxidation of chloropropene according to claim 1, wherein the amount of the catalyst used in step 2 is 0.01 to 0.99g/mol of hydrogen peroxide.
6. The method for continuously preparing epichlorohydrin by one-step epoxidation of chloropropene according to claim 5, wherein the amount of the catalyst used in step 2 is 0.10-0.50g/mol of hydrogen peroxide.
7. The method for continuously preparing epichlorohydrin by one-step epoxidation of chloropropene according to claim 1, wherein the molar ratio of chloropropene to hydrogen peroxide in step 2 is 2-4: 1.
8. The method for continuously preparing epichlorohydrin by one-step epoxidation of chloropropene according to claim 7, wherein the mol ratio of chloropropene to hydrogen peroxide in step 2 is 2.5-3.5: 1.
9. The method for continuously preparing epichlorohydrin by one-step epoxidation of chloropropene according to claim 1, wherein the hydrogen peroxide concentration in step 2 is 10-80 wt%.
10. The method for continuously preparing epichlorohydrin by one-step epoxidation of chloropropene according to claim 9, wherein the hydrogen peroxide concentration in step 2 is 30-70 wt%.
11. The process for the continuous preparation of epichlorohydrin by one-step epoxidation of chloropropene according to claim 1, wherein the reaction temperature in step 2 is 10-80 ℃.
12. The process for the continuous preparation of epichlorohydrin by one-step epoxidation of chloropropene according to claim 11, wherein the reaction temperature in step 2 is 30-60 ℃.
13. The process for continuously preparing epichlorohydrin by one-step epoxidation of chloropropene according to claim 1, wherein the retention time of the material in the reaction zone in the step 2 is 1-10 min.
14. The process for the continuous preparation of epichlorohydrin by one-step epoxidation of chloropropene according to claim 13, wherein the retention time of the material in the reaction zone in the step 2 is 2-5 min.
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| 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 |
| CN115385873B (en) * | 2022-10-25 | 2023-01-03 | 山东华夏神舟新材料有限公司 | Continuous synthesis method of perfluoro-2, 3-epoxy-2-methylpentane |
| 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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| CN102875494B (en) * | 2012-10-15 | 2015-08-26 | 常州大学 | A kind of method adopting micro passage reaction synthesizing epoxy chloropropane |
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