CN112047904A - Method for preparing cyclohexene oxide by using microchannel reactor - Google Patents
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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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- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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Abstract
The invention provides a method for preparing cyclohexene oxide by using a microchannel reactor, which comprises the following steps: dissolving a peroxide stabilizer in hydrogen peroxide to obtain a solution A; dissolving cyclohexene and carboxylic acid in an organic solvent to obtain a solution B; and respectively introducing the solution A and the solution B into a microchannel reactor for reaction to obtain a target product, namely cyclohexene oxide. The invention provides a method for preparing cyclohexene oxide by using a microchannel reactor, which realizes the coupling of two steps of synthesis of peroxycarboxylic acid and oxidation of cyclohexene, simplifies the process flow, has short reaction time, reduces the production cost and is easy for industrial amplification.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for preparing cyclohexene oxide by using a microchannel reactor.
Background
Cyclohexanoxide is a clear liquid with a characteristic odor, boiling point 129 ℃, relative density (4 ℃)0.996 and flash point 27.3 ℃. Insoluble in water, and soluble in organic solvent such as ethanol, diethyl ether, and acetone. The epoxy cyclohexane molecule contains a ternary oxygen-containing ring structure, has active chemical property, and is easy to open the ring under the action of an acid or alkali catalyst, and generates an addition reaction with water, alcohol, ammonia (amine), phenol or carboxylic nucleophilic substances to generate an intermediate.
The market application of cyclohexene oxide is extremely wide. Under the catalytic action of inorganic acid, the epoxy cyclohexane can rapidly generate hydrolysis reaction with water to generate 1, 2-cyclohexanediol. The cyclohexanediol is not only an intermediate for producing dyes, pesticides, resins, medicines and the like, but also a raw material for preparing high-grade epoxy resin diluents.
The pesticide propargite can be prepared by taking epoxy cyclohexane as a raw material. The acaricide has the advantages of high acaricidal efficiency, low toxic action on human bodies and plants, long effective time, low cost and the like, and is the preferred acaricide for controlling acarid pests of farmers.
The epoxy cyclohexane with extremely low viscosity can be used as a reactive diluent of epoxy resin, has strong dissolving capacity to the epoxy resin and has extremely low viscosity, so that the epoxy cyclohexane can be used as the reactive diluent of the epoxy resin to reduce the viscosity of the epoxy resin before curing and improve the flow property of the epoxy resin so as to facilitate casting and molding. Epoxycyclohexane is a reactive diluent, and when the epoxy resin is cured, the epoxycyclohexane also undergoes epoxy ring-opening polymerization reaction to form a part of the polymer with a network structure. The obtained epoxy resin is superior to epoxy resins treated with other reactive diluents in terms of the physical properties such as mechanical strength, heat resistance, electrical insulation, and aging resistance. In the presence of photosensitive catalyst, the epoxy cyclohexane can initiate cationic ring-opening polymerization reaction by ultraviolet irradiation, so as to prepare the photosensitive adhesive or the photosensitive coating. The key point of the process is the preparation of a photosensitive catalyst with excellent performance, and a diazonium salt catalyst, an iodonium salt or sulfonium salt catalyst and an aryl silane-organic aluminum series catalyst appear in sequence. However, the diazonium salt catalyst, iodonium salt or sulfonium salt catalyst, has poor catalytic performance. The former can initiate reaction at a place where no light is visible, which is inconvenient, while the iodonium salt or sulfonium salt catalyst, also called as "strong acid catalyst", can initiate polymerization of cyclohexene oxide under the irradiation of ultraviolet rays, but generates strong lewis acid which corrodes the metal surface during the reaction, thereby reducing the electrical insulation of the polymer; the occurrence of the aryl silane-organic aluminum catalyst series catalyst completely overcomes the defects of the two catalysts, and a small amount of aryl silane-organic aluminum catalyst can be subjected to high-efficiency reaction, so that the catalyst is a catalyst with excellent performance. The target product prepared by the method can be used for bonding and coating of common instruments and can also be used for precise instruments. At present, the epoxycyclohexane can be prepared by an oxygen oxidation method, a chlorohydrin method, an organic peroxyacid method, a hydrogen peroxide method, an alkyl peroxide method, an electrochemical epoxidation method, or the like.
Oxygen is cheap and convenient in source, is the most ideal oxygen source for oxidation reaction, and epoxidation reaction using air or oxygen as the oxygen source is also the traditional method for synthesizing epoxide. However, since molecular oxygen has a stable structure, it is difficult to epoxidize cyclohexene by directly using oxygen, and a special catalyst is required. In general, epoxidation reactions using molecular oxygen directly have poor selectivity. In a system without reducing agent, the reaction efficiency is low and the selectivity is poor. In a reducing agent system, the cost of the reducing agent is high, and the stability of the catalyst is poor. Therefore, the research on the molecular oxygen epoxidation is slow.
The cyclohexane oxidation method is a representative method, and a light fraction containing epoxy cyclohexane with the mass fraction of about 30% is generated in the process of preparing cyclohexanone and cyclohexanol by oxidizing cyclohexane, and is commonly called light oil. The recovery of cyclohexene oxide from light oils is one of the important sources from which it is obtained. However, in this method, epoxycyclohexane is a by-product, and the yield thereof is greatly restricted. Because of the improvement of the caprolactam production process, the process for preparing cyclohexanone by oxidizing cyclohexane lags behind, and the method can not realize large-scale production.
The japanese patent first reported that cyclohexene oxide was prepared from cyclohexene by the hypochlorous acid oxidation process. The hypochlorous acid in the reaction system is prepared by reacting sodium hypochlorite solution with dilute sulfuric acid, and is firstly obtained by reacting cyclohexene with the dilute sulfuric acid. The obtained hypochlorous acid is subjected to electrophilic addition reaction to generate o-chlorocyclohexanol, and then the o-chlorocyclohexanol is treated by sodium hydroxide to remove hydrogen chloride in a ring manner, so that the cyclohexene oxide is obtained. The selectivity of the target product o-chlorocyclohexanol in the olefin and hypochlorous acid addition step was about 84%. The chlorohydrin method is a domestic main production method, but the chlorohydrin method generates a large amount of wastes such as salt-containing wastewater, generates about 20 tons of wastewater when one ton of cyclohexene oxide is produced, has high energy consumption and serious equipment corrosion, and cannot meet the domestic gradually-improved environmental protection standard.
The hydrogen peroxide is an oxidant widely applied by people in recent years, the price is low, the environment is friendly, and an oxidation product is water which is non-toxic, harmless and pollution-free, and accords with the development trend of current green chemistry. Thus, hydrogen peroxide is often referred to as a "green" oxidizing agent. When the epoxy cyclohexane is prepared by using hydrogen peroxide as an oxidant, the preparation needs to be carried out under the condition of a proper catalyst. At present, effective catalysts are known as titanium silicalite molecular sieves, phosphotungstic acid and the like.
The titanium silicalite molecular sieve is widely applied to organic synthesis, the microporous titanium-containing molecular sieve has the advantages of good activity, high selectivity and greenness when being applied to the epoxidation of micromolecular olefin, and the problem of low selectivity exists in the prior method for producing cyclohexene oxide by using a titanium silicalite molecular sieve catalyst. The heteropoly acid catalyst generally refers to heteropoly acid and its salt, which is a polyoxometallate metal complex that is spatially combined by a central atom (i.e. heteroatom, P, Si, etc.) and coordination atoms (i.e. polyatomic, Mo, W, etc.) through an oxygen atom bridging mode, and besides acidity, the heteropoly acid is also a multi-electron body and has strong oxidation and reduction properties. The phase transfer catalyst has the advantages of simple structure, high catalytic activity, high product selectivity and the like, but the phase transfer catalyst has the defects of high product impurity content, difficult catalyst separation and the like.
In addition to catalytic oxidation, a peroxide oxidation method is also proposed, cyclohexene is oxidized into cyclohexene oxide by using peroxides such as hydrogen peroxide, tert-butyl peroxide, organic peroxy acid and the like, the peroxycarboxylic acid has a simple structure and is low in price, and the cyclohexene oxide prepared by oxidizing the cyclohexene has the advantages of mild reaction conditions, controllability, high product selectivity and the like.
Currently, alkyl hydroperoxides, which are widely used and have high stability, are mainly t-butyl hydroperoxide (t-BuOOH) and Cumyl Hydroperoxide (CHP). The peroxide requires that the oxidant does not contain alpha-H, and has the characteristics of mild reaction, convenient control, high yield, good catalytic selectivity and the like. However, these organic peroxides are unstable and cannot be stored and transported for a long period of time, and therefore, they need to be prepared on site, and when used for production, an organic peroxide production apparatus needs to be established, which results in high base costs.
In the epoxidation of cyclohexene using these substances as oxidants, the catalyst species used are mainly higher-valent transition metal complexes, such as ti (iv), v (v), mo (vi), etc., or other transition metal complexes. In the high-valence transition metal complex, Mo (VI) is a catalyst with higher cyclohexene epoxidation catalytic activity, and the property of a ligand (L) in the Mo complex has a larger influence on the catalytic performance, wherein the Mo-L bond is too strong, so that the activity of the catalyst is reduced, the bond is too weak, the selectivity is reduced, and therefore, a proper ligand must be selected to obtain more ideal catalytic performance. Taking tert-butyl peroxide as an example, taking a reaction product of molybdenum metal powder adsorbed on activated carbon and hydrogen peroxide to catalyze cyclohexene oxidation, the product is only cyclohexene oxide, and the activity of the loaded catalyst is improved by about 6 times compared with that of the unloaded catalyst. The epoxidation of cyclohexene by molybdenum acetate catalysis gave cyclohexene oxide yields close to the theoretical values, calculated as t-BuOOH. The molybdenum complex catalyst has excellent catalytic activity and selectivity. In addition to Mo complexes, molybdenum acetylacetonate, titanium acetylacetonate, and the like are also excellent species for catalyzing olefin epoxidation, but they are inferior to molybdenum salts in catalytic activity and selectivity. In addition, homogeneous catalysts can be supported to convert the homogeneous catalysts into heterogeneous reactions, and various carriers can be used for supporting the heterogeneous catalysts. Typically, the catalyst can be supported by grafting the catalyst to carriers such as polystyrene resin, organic chelating resin, polybenzimidazole, polythioether amino acid cross-linked resin, ion exchange resin, phosphocellulose, surface-modified silica gel and the like through ligand exchange. When organic peroxyacids are used as the oxidizing agent, common organic peroxyacids such as peroxyformic acid, peroxyacetic acid, peroxybenzoic acid and the like have the advantages of easiness in preparation, low price and the like, can generate epoxidation reaction with various double bond structures, and have the defects of instability, easiness in decomposition and inconvenience in storage under the condition of single existence of the peroxyacids, and are usually directly used without separation after being prepared by using hydrogen peroxide.
The process for preparing cyclohexene oxide by oxidizing cyclohexene with peroxycarboxylic acid is realized by a two-step method, firstly, carboxylic acid and hydrogen peroxide are subjected to peroxidation reaction to obtain peroxycarboxylic acid, and the reaction formula is as follows: ROOH + H2O2＝ROOOH+H2O; then, the peroxycarboxylic acid and cyclohexene are subjected to oxidation reaction to obtain cyclohexene oxide, wherein the reaction formula is as follows: ROOOH + C6H10＝ROOH+C6H10O; however, the two-step reaction conditions are greatly different, the synthesis of peroxycarboxylic acid requires higher temperature, and the target product cyclohexene oxide is unstable in chemical property and easy to decompose. In order to prevent decomposition of the epoxycyclohexane product, the reaction for synthesizing epoxycyclohexane requires a relatively low temperature, and therefore, the reaction conditions need to be strictly controlled. In general, the synthesis of epoxycyclohexane by the peroxycarboxylic acid method requires two steps, namely synthesis of peroxycarboxylic acid and oxidation of cyclohexene. The peroxycarboxylic acid has the problems of instability, difficult long-time storage and need of preparation in situ, so that the reaction process is complex and difficult to control.
Micro-reactors, micro-structured reactors, microchannel reactors refer to chemical reactions that can be completed in a range of lateral dimensions less than 1mm, and the most typical representation of such structures is microchannels. Microchannel reactors are a discipline in the field of micro-machining engineering, and this device (such as a micro-heat exchanger) is accompanied by some physical reactions. Such microchannel reactors are typically continuous flow reactors (as opposed to batch reactors). Compared with the conventional reaction equipment, the microchannel reactor has advantages in many aspects, such as heat exchange efficiency, reaction speed, yield, safety, stability, monitoring performance, on-site/on-demand production and capability of more refined production control. The micro-channel reactor equipment has extremely large specific surface area due to the internal microstructure, which can reach hundreds of times or even thousands of times of the specific surface area of the stirring kettle. The microchannel reactor has excellent heat transfer and mass transfer capacity, can realize instantaneous uniform mixing of materials and high-efficiency heat transfer, and therefore, many reactions which cannot be realized in the conventional reactor can be realized in the microchannel reactor.
By using the microchannel reactor, the reaction temperature can be accurately controlled, especially for reactions with significant thermal effects. Meanwhile, the microchannel reactor has higher safety factor, the continuous flow microchannel reactor has small liquid holdup, is different from the real-time reaction amount of a traditional reaction kettle taking tons as a unit, has small effective volume in the reactor, is equivalent to that substances which generate chemical reaction at each moment in the reactor are only a few milliliters to a few liters, has controllable safety risk, and is suitable for treating peroxidation and epoxidation.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a method for preparing cyclohexene oxide by using a microchannel reactor, which realizes the coupling of two steps of synthesis of peroxycarboxylic acid and oxidation of cyclohexene and simplifies the process flow.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a method for preparing cyclohexene oxide by using a microchannel reactor comprises the following steps: dissolving a peroxide stabilizer for stabilizing peroxide in hydrogen peroxide to obtain a solution A; dissolving cyclohexene and carboxylic acid in an organic solvent to obtain a solution B; and respectively introducing the solution A and the solution B into a microchannel reactor for reaction to produce cyclohexene oxide, and finally collecting a product at the tail of the reactor.
Further, the peroxide stabilizer is one or more of sodium silicate, magnesium fatty acid, polyacrylamide, stannous chloride, sodium phosphate, sodium tripolyphosphate, sodium polyphosphate, tetraethyl diamine, disodium ethylene diamine tetraacetate, sodium diethylamine pentaacetate, citric acid, tartaric acid and the like, and preferably one or a mixture of two of sodium silicate and disodium ethylene diamine tetraacetate; the concentration of the peroxide stabilizer in the solution A is 0.02-2%, preferably 0.1-0.5%.
Further, the organic solvent is one or more of benzene, toluene, cyclohexane, n-hexane, acetonitrile, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl chloride, dichloromethane, dichloroethane, dimethyl sulfoxide, methanol, ethanol, acetone, diethyl ether, tetrahydrofuran, and the like, and preferably one or a mixture of two of ethyl acetate and dichloromethane.
Further, the carboxylic acid is one or more of formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, oleic acid, oxalic acid, malonic acid, adipic acid, benzoic acid, salicylic acid, citric acid and the like, and preferably one or a mixture of two of acetic acid and propionic acid; the concentration of the carboxylic acid in the solution B is 0.1-60%, preferably, the concentration of the carboxylic acid in the solution B is 20-40%.
Further, the hydrogen peroxide is hydrogen peroxide with the concentration of 30-70%, and preferably hydrogen peroxide with the concentration of 55-65%.
Further, the concentration of cyclohexene in the solution B is 20-80%, and preferably 25-40%.
Further, the flow rate ratio of the solution A to the solution B introduced into the microchannel reactor is 1: 1-1: 10, preferably 1: 3-1: 6.
Further, the reaction temperature of the microchannel reactor is 50-150 ℃, and preferably 65-120 ℃; the reaction pressure is 50-5000 kpa, preferably 1000-2000 kpa; the reaction time is 10 to 500s, preferably 30 to 100 s.
Compared with the prior art, the method for preparing cyclohexene oxide by using the microchannel reactor has the following advantages: the microchannel reactor is adopted to realize the step coupling of the synthesis of peroxycarboxylic acid and the oxidation of cyclohexene, the process flow is simplified, the reaction is rapid, the reaction time is short, the reaction condition is mild, the safety is high, the adopted raw materials are simple, the price is low, the production cost is reduced, and the industrial amplification is easy; meanwhile, the method has higher conversion rate and high selectivity.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Dissolving disodium ethylene diamine tetraacetate into 55% hydrogen peroxide to prepare solution A, wherein the concentration of the disodium ethylene diamine tetraacetate in the solution A is 0.1%; adding cyclohexene and acetic acid into dichloromethane to prepare a solution B, wherein the concentration of the cyclohexene in the solution B is 25% and the concentration of the acetic acid is 30%; and (3) introducing the solution A and the solution B into a microchannel reactor according to the flow rate ratio of 1:4, wherein the reaction time is 60s, the temperature of the reactor is 105 ℃, the pressure is 1500kpa, collecting a product at the tail part of the microchannel reactor, the conversion rate of cyclohexene in the product is 83.12%, the selectivity of cyclohexene oxide is 93.73%, and the utilization rate of hydrogen peroxide is 68.23%.
Example 2
Dissolving sodium phosphate in 65% hydrogen peroxide to prepare solution A, wherein the concentration of the sodium phosphate in the solution A is 0.3%; adding cyclohexene and acetic acid into ethyl acetate to prepare a solution B, wherein the concentration of the cyclohexene in the solution B is 20% and the concentration of the acetic acid is 25%; and (3) introducing the solution A and the solution B into a microchannel reactor according to the flow rate ratio of 1:6, wherein the reaction time is 30s, the temperature of the reactor is 120 ℃, the pressure is 1500kpa, collecting a product at the tail part of the microchannel reactor, the conversion rate of cyclohexene in the product is 79.34%, the selectivity of cyclohexene oxide is 86.63%, and the utilization rate of hydrogen peroxide is 78.23%.
Example 3
Dissolving sodium silicate in 55% hydrogen peroxide to prepare solution A, wherein the concentration of the sodium silicate in the solution A is 0.1%; adding cyclohexene and propionic acid into ethyl acetate to prepare a solution B, wherein the concentration of the cyclohexene in the solution B is 30% and the concentration of the propionic acid is 40%; and (3) introducing the solution A and the solution B into a microchannel reactor according to the flow rate ratio of 1:3, wherein the reaction time is 65s, the temperature of the reactor is 100 ℃, the pressure is 2000kpa, and collecting a product at the tail part of the microchannel reactor, wherein the conversion rate of cyclohexene in the product is 97.45%, the selectivity of cyclohexene oxide is 96.73%, and the utilization rate of hydrogen peroxide is 84.86%.
Example 4
Dissolving disodium ethylene diamine tetraacetate into 65% hydrogen peroxide to prepare solution A, wherein the concentration of the disodium ethylene diamine tetraacetate in the solution A is 0.1%; adding cyclohexene and benzoic acid into acetonitrile to prepare a solution B, wherein the concentration of the cyclohexene in the solution B is 40% and the concentration of the benzoic acid is 20%; and (3) introducing the solution A and the solution B into a microchannel reactor according to the flow rate ratio of 1:3, wherein the reaction time is 200s, the temperature of the reactor is 120 ℃, the pressure is 1100kpa, and collecting a product at the tail part of the microchannel reactor, wherein the conversion rate of cyclohexene in the product is 67.73%, the selectivity of cyclohexene oxide is 94.01%, and the utilization rate of hydrogen peroxide is 65.63%.
Example 5
Dissolving sodium silicate in 30% hydrogen peroxide to prepare solution A, wherein the concentration of the sodium silicate in the solution A is 0.1%; adding cyclohexene and propionic acid into ethyl acetate to prepare a solution B, wherein the concentration of the cyclohexene in the solution B is 30% and the concentration of the propionic acid is 40%; and (3) introducing the solution A and the solution B into a microchannel reactor according to the flow rate ratio of 1:1, wherein the reaction time is 500s, the temperature of the reactor is 100 ℃, the pressure is 1000kpa, and collecting a product at the tail part of the microchannel reactor, wherein the conversion rate of cyclohexene in the product is 87.35%, the selectivity of cyclohexene oxide is 45.94%, and the utilization rate of hydrogen peroxide is 86.36%.
Example 6
Dissolving sodium tripolyphosphate in 50% hydrogen peroxide to prepare solution A, wherein the concentration of the sodium tripolyphosphate in the solution A is 0.1%; adding cyclohexene and benzoic acid into ethyl acetate to prepare a solution B, wherein the concentration of the cyclohexene in the solution B is 30% and the concentration of the benzoic acid is 10%; and (3) introducing the solution A and the solution B into a microchannel reactor according to the flow rate ratio of 1:4, wherein the reaction time is 100s, the temperature of the reactor is 110 ℃, the pressure is 1000kpa, and collecting a product at the tail part of the microchannel reactor, wherein the conversion rate of cyclohexene in the product is 86.12%, the selectivity of cyclohexene oxide is 79.24%, and the utilization rate of hydrogen peroxide is 91.12%.
Comparative example 1
Disodium ethylene diamine tetraacetate, hydrogen peroxide, cyclohexene and propionic acid are dissolved in ethyl acetate to prepare a solution, wherein the concentration of the disodium ethylene diamine tetraacetate is 0.05%, the concentration of the hydrogen peroxide is 30%, the concentration of the cyclohexene is 20%, and the concentration of the propionic acid is 15%. The solution is placed in a reaction kettle, the reaction kettle is heated to 100 ℃ and the pressure is 1000kpa, the reaction kettle is rapidly cooled after the reaction is finished, the conversion rate of cyclohexene in the product is 78.41%, the selectivity of cyclohexene oxide is 3.41%, and the utilization rate of hydrogen peroxide is 97.41%.
Comparative example 2
Taking 60% hydrogen peroxide as A solution; dissolving cyclohexene in propionic acid and adding to prepare a solution B, wherein the concentration of the cyclohexene in the solution B is 50%; and (3) introducing the solution A and the solution B into a microchannel reactor according to the flow rate ratio of 1:2, wherein the reaction time is 100s, the temperature of the reactor is 110 ℃, the pressure is 1000kpa, and collecting a product at the tail part of the microchannel reactor, wherein the conversion rate of cyclohexene in the product is 91.14%, the selectivity of cyclohexene oxide is 3.91%, and the utilization rate of hydrogen peroxide is 91.52%.
As can be seen from examples 1-6 and comparative example 1, the coupling of two steps of preparing cyclohexene oxide by oxidizing cyclohexene with peroxycarboxylic acid is realized by using a microchannel reactor as a reactor, and the cyclohexene oxide has high selectivity and high conversion rate; as can be seen from the comparative example 2, the target cyclohexene oxide is unstable in chemical property and easy to decompose when heated, and the addition of the peroxide stabilizer can effectively stabilize the cyclohexene oxide and inhibit the decomposition of the cyclohexene oxide; meanwhile, the whole process steps are simple, and the reaction time is short.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for preparing cyclohexene oxide by using a microchannel reactor is characterized by comprising the following steps: dissolving a peroxide stabilizer in hydrogen peroxide to obtain a solution A; dissolving cyclohexene and carboxylic acid in an organic solvent to obtain a solution B; and respectively introducing the solution A and the solution B into a microchannel reactor for reaction to obtain a target product, namely cyclohexene oxide.
2. The process of claim 1 for preparing epoxycyclohexane using a microchannel reactor, wherein: the peroxide stabilizer is one or more of sodium silicate, magnesium fatty acid, polyacrylamide, stannous chloride, sodium phosphate, sodium tripolyphosphate, sodium polyphosphate, tetraethyl diamine, disodium ethylene diamine tetraacetate, sodium diethylamine pentaacetate, citric acid, tartaric acid and the like, and preferably one or a mixture of two of sodium silicate and disodium ethylene diamine tetraacetate.
3. The process of claim 1 for preparing epoxycyclohexane using a microchannel reactor, wherein: the concentration of the peroxide stabilizer in the solution A is 0.02-2%, preferably 0.1-0.5%.
4. The process of claim 1 for preparing epoxycyclohexane using a microchannel reactor, wherein: the organic solvent is one or more of benzene, toluene, cyclohexane, n-hexane, acetonitrile, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl chloride, dichloromethane, dichloroethane, dimethyl sulfoxide, methanol, ethanol, acetone, diethyl ether, tetrahydrofuran, and the like, and preferably one or a mixture of two of ethyl acetate and dichloromethane.
5. The process of claim 1 for preparing epoxycyclohexane using a microchannel reactor, wherein: the carboxylic acid is one or more of formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, oleic acid, oxalic acid, malonic acid, adipic acid, benzoic acid, salicylic acid, citric acid and the like, and one or two of acetic acid and propionic acid are preferably mixed.
6. The process of claim 1 for preparing epoxycyclohexane using a microchannel reactor, wherein: the hydrogen peroxide is hydrogen peroxide with the concentration of 30-70%, and preferably hydrogen peroxide with the concentration of 55-65%.
7. The process of claim 1 for preparing epoxycyclohexane using a microchannel reactor, wherein: the concentration of the carboxylic acid in the solution B is 0.1-60%, preferably, the concentration of the carboxylic acid in the solution B is 20-40%.
8. The process of claim 1 for preparing epoxycyclohexane using a microchannel reactor, wherein: the concentration of cyclohexene in the solution B is 20-80%, and the preferable concentration is 25-40%.
9. The process of claim 1 for preparing epoxycyclohexane using a microchannel reactor, wherein: the flow rate ratio of the solution A to the solution B introduced into the microchannel reactor is 1: 1-1: 10, and preferably 1: 3-1: 6.
10. The process of claim 1 for preparing epoxycyclohexane using a microchannel reactor, wherein: the reaction temperature of the microchannel reactor is 50-150 ℃, and preferably 65-120 ℃; the reaction pressure is 50-5000 kpa, preferably 1000-2000 kpa; the reaction time is 10 to 500s, preferably 30 to 100 s.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113372300A (en) * | 2021-06-07 | 2021-09-10 | 浙江聚贤医药科技有限公司 | Continuous flow synthesis process of cyclohexene-based epoxide and cyclohexene-based epoxide |
| CN114315761A (en) * | 2021-11-22 | 2022-04-12 | 浙江巨化技术中心有限公司 | Continuous preparation method of hexafluoropropylene tripolymer epoxide |
| CN116063251A (en) * | 2023-01-06 | 2023-05-05 | 陕西煤业化工技术研究院有限责任公司 | Method for preparing epoxy compound by utilizing microchannel reactor |
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| CN116063251A (en) * | 2023-01-06 | 2023-05-05 | 陕西煤业化工技术研究院有限责任公司 | Method for preparing epoxy compound by utilizing microchannel reactor |
| CN116063251B (en) * | 2023-01-06 | 2024-05-14 | 陕西煤业化工技术研究院有限责任公司 | Method for preparing epoxy compound by utilizing microchannel reactor |
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