Continuous production method and system of oxidized cycloolefin and application

Abstract

The invention discloses a continuous production method and system of oxidized cycloolefin and application, and belongs to the technical field of cyclic olefin ring preparation. According to the method disclosed by the invention, the raw material cycloolefin is used for replacing an additional solvent to dissolve the catalyst, the complicated preparation process is simplified, the oxide quenching reaction is adopted in the preparation process to realize quenching of peroxide in a reaction system, the potential safety hazard caused by the peroxide is effectively avoided, and in the oxide quenching reaction process, due to the addition of the quenching agent, the reaction efficiency is greatly improved. The solubility of oxidized cycloolefin in water can be reduced, a centrifugal extraction section is used in a matched mode, organic matter in water can be recycled to the maximum extent, the product yield is increased, an extracting agent can be azeotropic with water, the moisture content of oxidized cycloolefin can be remarkably reduced in the subsequent rectification section, and the quality of oxidized cycloolefin is improved. The technical problems of low yield and low quality of oxidized cycloolefin in the prior art are solved.

Description

Technical Field

[0001] The invention belongs to the technical field of cyclic olefin ring preparation, and specifically relates to a continuous production method, system and application of oxidized cyclic olefin. Background Art

[0002] As an important organic synthesis intermediate, cycloolefin oxides are widely used in petrochemicals, fine chemicals and organic synthesis, and play an important role in the national economy. Due to the polarization of the charge in the epoxy group and the presence of tension in the oxygen-heterocyclic ring, the epoxy group has a high reactivity and is easy to react with groups containing active hydrogen such as amine, hydroxyl, phenolic hydroxyl, carboxyl, amide, etc. to synthesize a series of high value-added compounds.

[0003] Cyclohexene oxide is an important fine chemical. Its ternary epoxy structure is very active and can be used to prepare a large number of intermediates by ring opening. It is an important raw material for synthesizing benzhexol hydrochloride, pesticides tricyclotin, propargite, 1,2-cyclohexanediol, polycarbonate, dicarboxylic acid glycerol ether, etc. It is widely used in the fields of medicine, pesticides, plasticizers, diluents and surfactants.

[0004] Cyclopentene oxide, also known as 1,2-epoxycyclopentane, is an important organic synthesis intermediate. It is widely used in organic synthesis reactions and can also be used to prepare synthetic resins, coatings, plastics, rubber and other materials.

[0005] Limonene oxide is an organic compound, a colorless oily liquid, chemically belonging to the monoterpenoid class of compounds, with an epoxy group and an unsaturated ring structure. Due to its unique chemical properties, limonene oxide has a unique fresh citrus aroma and is often used in the perfume and fragrance industry. As an important organic synthesis intermediate, limonene oxide can be used to synthesize a variety of drug molecules. Limonene oxide is also used as a food additive, especially in beverages and dairy products to provide specific flavors.

[0006] Microchemical technology aims to promote the continuity, greenness and safety of chemical processes. It is a typical representative of new chemical productivity and a new chemical technology direction that has attracted extensive attention from academia and industry. It has great advantages over traditional reactors. For example, in terms of safety, it has excellent mass and heat transfer efficiency and small online liquid volume, which can effectively increase the safety of hazardous chemical processes such as oxidation, chlorination, hydrogenation, and nitration; in terms of experiments, it has the advantages of easy scale-up and short R&D cycle. The R&D results of small tests can be directly scaled up for production without amplification effect, which greatly saves R&D costs; continuous reactions replace intermittent reactions, reaction conditions are easy to control, and reaction efficiency is significantly improved.

[0007] The Chinese patent application with publication number CN 101613330 A discloses a heteropolyacid catalyst containing phosphotungsten. This technical solution not only uses a large amount of toxic solvents, but also has the problems of large catalyst dosage and low recovery rate. The Chinese patent application with publication number CN 103272649 A discloses a method for preparing a two-phase catalyst containing tungsten boron and its application in the epoxidation of cyclohexene to prepare oxidized cyclohexene. This process has the problem of low cyclohexene conversion rate. The Chinese patent application with publication number CN 1127422444 A discloses a method for catalyzing olefin epoxidation with titanium-containing mesoporous molecular sieves. This technical solution has the problems of low selectivity of oxidized cycloolefins and complicated catalyst preparation process. The Chinese patent application with publication number CN 115888828A discloses a phosphorus-boron doped tungsten-molybdenum catalyst, a preparation method thereof and application in olefin epoxidation. The technology developed by this technical solution has the advantages of small catalyst dosage, low catalyst production cost, catalyst solubility in various solvents without the presence of peroxide, strong universality of reaction substrates, low reaction temperature, low safety risk, high reaction conversion rate and high selectivity.

[0008] The Chinese patent application with publication number CN 109534103 A discloses a method using a microchannel, in which a two-phase catalyst containing tungsten and boron is mixed with materials in a microchannel reactor and then an epoxidation reaction is carried out through a tubular reactor. This method has certain safety risks due to the easy precipitation of the catalyst, which easily causes pipeline blockage, and the catalyst recovery rate is extremely low. The Chinese patent application with publication number CN 116063251 A discloses a method for preparing oxidized cycloolefins using a microchannel reactor. This method only achieves intrinsic safety in the reaction stage, and does not study the safety risks of the reaction materials in the refining aspect. The trace peroxides present in the material system have certain explosion risks in actual production.

[0009] In the prior art, the peroxide in the reaction system has an explosion risk during the refining process of the oxidized cycloolefin. The safety hazard can only be eliminated by completely quenching the peroxide in the reaction system before refining the oxidized olefin. The quenching reaction of the peroxide is an exothermic reaction, which easily leads to the ring-opening reaction of the ternary epoxy group of the oxidized cycloolefin, affecting the yield and quality of the oxidized cycloolefin. Summary of the invention

[0010] The object of the present invention is to provide a continuous production method, system and application of oxidized cycloolefins, so as to solve the technical problem of low yield in the existing oxidized cycloolefin preparation methods.

[0011] In order to achieve the above object, the present invention adopts the following technical solutions: The present invention discloses a continuous production method of oxidized cycloolefins, comprising the following steps: After mixing the disodium hydrogen phosphate solution and the catalyst solution of the cycloolefin, an epoxidation reaction is carried out to obtain a reaction product; After mixing the reaction product and a saturated aqueous solution of a quenching agent, a peroxide quenching reaction is performed to obtain a post-reaction material; The obtained reaction material is subjected to centrifugal extraction to obtain an organic phase and an aqueous phase. The organic phase is subjected to rectification to obtain oxidized cycloolefins.

[0012] Further, the epoxidation reaction temperature is 25-35°C, and the reaction time is 1.0-2.0 min; The temperature of the oxide quenching reaction is 25-35° C., and the reaction time is 10-30 seconds.

[0013] Furthermore, the vacuum degree of the distillation is -10-15 mbar, and the temperature is 35-70°C.

[0014] Furthermore, the dosage ratio of the disodium hydrogen phosphate solution and the cycloolefin catalyst solution is 1 g: (0.83-1) g; The disodium hydrogen phosphate solution is obtained by mixing disodium hydrogen phosphate and hydrogen peroxide; the concentration of the disodium hydrogen phosphate solution is 3.85-4.5 g / mL; the cycloolefin catalyst solution is obtained by dissolving the catalyst in the cycloolefin; the concentration of the cycloolefin catalyst solution is 3.57 g-4.5 / mL; The mass ratio of the reaction product to the saturated aqueous solution of the quencher is 1.00 g: ((0.003-0.03) g); The saturated aqueous solution of the quenching agent is one of sodium thiosulfate, sodium bisulfite and potassium bisulfite.

[0015] Further, the cycloolefin is one of cyclohexene, cyclopentene and limonene; the catalyst is a boron-phosphorus doped tungsten-molybdenum catalyst; The boron-phosphorus doped tungsten-molybdenum catalyst is: (C 4 H 12 N) 3 BPW 4.5 Mo 4.5 O 30 , (C 16 H 36 N) 3 BPW 4.5 Mo 4.5 O 30 , (C 22 H 48 N) 3 BPW 4.5 Mo 4.5 O 30 ,(C38 H 80 N) 3 BPW 4.5 Mo 4.5 O 30 , (C 11 H 26 N) 3 BPW 4.5 Mo 4.5 O 30 , (C 13 H 30 N) 3 BPW 4.5 Mo 4.5 O 30 , (C 21 H 46 N) 3 BPW 4.5 Mo 4.5 O 30 and (C 19 H 42 N) 3 BPW 4.5 Mo 4.5 O 30 One or more of .

[0016] Furthermore, the centrifugal extraction is carried out after mixing the reaction material and the extractant, and the feed amount of the extractant is 2-3 mL / min; the extractant is one of dichloroethane, ethyl acetate, raw material cyclic olefin, benzene, cyclohexane and toluene.

[0017] The present invention also discloses a continuous production system of oxidized cycloolefins, comprising an epoxidation reaction raw material supply system, a peroxide quenching reaction raw material supply system, a centrifugal extraction raw material supply system, an epoxidation reaction module, a peroxide quenching reaction module, a centrifugal extraction module and a product collection module; The epoxidation reaction raw material supply system is connected to the inlet of the epoxidation reaction module, the outlet of the epoxidation reaction module is connected to the inlet of the peroxide quenching reaction module; the outlet of the peroxide quenching reaction module is connected to the outlet of the centrifugal extraction module; the outlet of the centrifugal extraction module is connected to the product collection module; The peroxide quenching reaction raw material supply system is connected to the inlet of the peroxide quenching reaction module; the centrifugal extraction raw material supply system is connected to the inlet of the centrifugal extraction module.

[0018] Further, the epoxidation reaction module is an epoxidation microreactor; the peroxide quenching reaction module is a peroxide quenching microreactor; the centrifugal extraction module is a centrifugal extractor; The epoxidation reaction raw material supply system is connected to the inlet of the epoxidation microreactor; a micro mixer is connected between the epoxidation reaction raw material supply system and the inlet of the epoxidation microreactor.

[0019] Further, the product collection module includes an organic phase collection system and an aqueous phase collection system; The organic phase outlet of the centrifugal extractor is connected to the organic phase collection system; the water phase outlet of the centrifugal extractor is connected to the water phase collection system; The organic phase collection system includes an online detection device, an organic phase storage tank, a distillation device and an oxidized cycloolefin storage tank; the water phase collection system is a water phase storage tank; The organic phase outlet of the centrifugal extractor is connected in sequence with a line detection device, an organic phase storage tank, a rectification device and an oxidized cycloolefin storage tank; The water phase outlet of the centrifugal extractor is connected to the water phase storage tank.

[0020] The present invention also discloses the application of the continuous production system of the oxidized cycloolefins, and the continuous production system of the oxidized cycloolefins is used to implement the production method.

[0021] Compared with the prior art, the present invention has the following beneficial effects: The invention discloses a continuous production method of oxidized cycloolefins. The raw material cycloolefins are used to replace additional solvents to dissolve catalysts, thereby simplifying the complicated preparation process. During the preparation process, an oxide quenching reaction is used to quench the peroxide in the reaction system, thereby effectively avoiding the potential safety hazards caused by the peroxides. During the oxide quenching reaction, the addition of a quenching agent can reduce the solubility of the oxidized cycloolefins in water. A centrifugal extraction section is used in conjunction with the quenching agent to maximize the recovery of organic matter in water and improve the product yield. The extractant can be azeotropic with water, and the water content of the oxidized cycloolefins can be significantly reduced in the subsequent distillation section, thereby improving the quality of the oxidized cycloolefins and solving the technical problems of low yield and quality of the oxidized cycloolefins in the prior art.

[0022] The present invention also discloses a continuous production system of oxidized cycloolefins. By arranging an epoxidation reaction raw material supply system, a peroxide quenching reaction raw material supply system, a centrifugal extraction raw material supply system, an epoxidation reaction module, a peroxide quenching reaction module, a centrifugal extraction module and a product collection module, the peroxide of the reaction system is in situ quenched in the epoxidation reaction module and the peroxide quenching reaction module, thereby avoiding the safety risk problem caused by the residual peroxide in the reaction system; combining the continuous centrifugal extraction technology and the distillation technology, a stable continuous safe production method of oxidized cycloolefins is provided, and the yield and product quality of the oxidized cycloolefins are improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1It is a schematic diagram of the composition of the continuous production system of oxidized cycloolefins of the present invention; Among them: 1-epoxidation reaction raw material supply system; 2-peroxide quenching reaction raw material supply system; 3-centrifugal extraction raw material supply system; 4-micro mixer; 5-epoxidation microreactor; 6-peroxide quenching microreactor; 7-centrifugal extractor; 8-online detection device; 9-organic phase storage tank; 10-distillation device; 11-oxidized cycloolefin storage tank; 12-aqueous phase storage tank. DETAILED DESCRIPTION

[0024] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the text are the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definition in this specification shall prevail.

[0025] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0026] In this article, all features such as values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have included and specifically disclosed all possible secondary ranges and individual values ​​within the range (including integers and fractions).

[0027] In this document, unless otherwise specified, “includes,” “including,” “contains,” “has,” or similar terms cover the meanings of “consisting of” and “mainly consisting of,” for example, “A includes a” covers the meanings of “A includes a and other” and “A only includes a.”

[0028] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.

[0029] The present invention provides a continuous production method of oxidized cycloolefins, comprising the following steps: Disodium hydrogen phosphate and hydrogen peroxide are prepared into a disodium hydrogen phosphate solution, a catalyst is dissolved in a cycloolefin to prepare a cycloolefin catalyst solution, a quenching agent is prepared into a quenching agent saturated aqueous solution, and an extracting agent is prepared for use; The disodium hydrogen phosphate solution and the catalyst solution of the cycloolefin are respectively introduced into the epoxidation microreactor 5 with an inner diameter of 2.5 mm by using metering pumps to complete the epoxidation reaction of the cycloolefin to obtain a reaction product; the reaction temperature is 25-35° C., and the retention time of the material in the reactor is 1.0-2.0 minutes; The saturated aqueous solution of the quenching agent is input into the peroxide quenching microreactor 6 by a metering pump and mixed with the reaction product to perform a peroxide quenching reaction to obtain a reacted material; the reaction temperature is 25-35° C.; the inner diameter and material of the oxide quenching microreactor 6 and the epoxidation microreactor 5 are consistent, and the retention time of the material in the reactor is 10-30 seconds; After the reaction, the material and the extractant enter the centrifugal extractor 7 for centrifugal extraction to obtain an organic phase and an aqueous phase. The aqueous phase enters the aqueous phase storage tank 12 for storage, and the organic phase enters the online detection device 8, the organic phase storage tank 9, and the distillation device 10 in sequence to finally obtain the oxidized cycloolefin and enter the oxidized cycloolefin storage tank 11 for storage.

[0030] like Figure 1 As shown, the present invention also discloses a continuous production system of oxidized cycloolefins, comprising an epoxidation reaction raw material supply system 1, a peroxide quenching reaction raw material supply system 2, a centrifugal extraction raw material supply system 3, an epoxidation microreactor 5, a peroxide quenching microreactor 6, and a centrifugal extraction module which is a centrifugal extractor 7; wherein, the epoxidation reaction raw material supply inlet is connected to the system 1 and the inlet of the epoxidation microreactor 5, the outlet of the epoxidation microreactor 5 is connected to the inlet of the peroxide quenching microreactor 6, the outlet of the peroxide quenching microreactor 6 is connected to the inlet of the centrifugal extraction module which is a centrifugal extractor 7, the organic phase outlet of the centrifugal extractor 7 is connected to the line detection device 8, the organic phase storage tank 9, the distillation device 10 and the oxidized cycloolefin storage tank 11 in sequence, and the water phase outlet of the centrifugal extractor 7 is connected to the water phase storage tank 12.

[0031] Preferably, a micro mixer 4 is connected between the epoxidation reaction raw material supply system 1 and the inlet of the epoxidation microreactor 5 .

[0032] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0033] The following examples use conventional instruments and equipment in the art. The experimental methods in the following examples where specific conditions are not specified are usually carried out under conventional conditions or under conditions recommended by the manufacturer. The various raw materials used in the following examples are conventional commercial products unless otherwise specified, and their specifications are conventional specifications in the art. In the specification of the present invention and the following examples, unless otherwise specified, "%" means weight percentage, "part" means weight part, and ratio means weight ratio.

[0034] Example 1 A continuous production method for oxidized cycloolefins comprises the following steps: At 20°C, 5 g of disodium hydrogen phosphate was mixed with 130 mL of 30% H 2 O 2 Prepare disodium hydrogen phosphate solution by adding 5 g of B 0.5 P 0.5 W 4.5 Mo 4.5 O 31 (C 4 H 12 N) 3 Dissolve in 140 mL of cyclohexene to prepare a cycloolefin catalyst solution; prepare the quenching agent into a saturated aqueous solution of the quenching agent at 25°C; take the extractant for later use; The sodium hydrogen phosphate solution and the catalyst of the cycloolefin are respectively introduced into the epoxidation microreactor 5 with an inner diameter of 2.5 mm by metering pumps to complete the epoxidation reaction of the cycloolefin to obtain a reaction product. The epoxidation reaction temperature is 60°C, the pressure is 0.2 MPa, and the reaction time is 1 min. Subsequently, the reacted material and the extractant are introduced into a centrifugal extractor 7 for centrifugal extraction to obtain an organic phase and an aqueous phase. The aqueous phase is stored in an aqueous phase storage tank 12, and the organic phase is sequentially introduced into an online detection device 8, an organic phase storage tank 9, and a distillation device 10 to finally obtain oxidized cycloolefins and enter an oxidized cycloolefin storage tank 11 for storage; the online detection device 8 analyzes that the content of oxidized cyclohexene in every 100 g of aqueous phase is 1.0 g; during the distillation process of the distillation device 10, the vacuum degree is -10 mbar, the tower bottom temperature is 35°C, and the oxidized cyclohexene is collected at the top of the tower by condensation; the yield of oxidized cyclohexene in this process is 97.9%, the purity is ≥ 99.5%, the peroxide content is 0.95%, and the moisture content is 0.15%; The dosage ratio of the disodium hydrogen phosphate solution and the cycloolefin catalyst solution is 1 g:0.83 g; The purity, moisture and other quality test methods of oxidized cycloolefins refer to the group standard of China Petrochemical and Chemical Industry Federation-T / CPCIF 000X-2021. The oxidized cycloolefins in the aqueous phase are detected by gas chromatography (internal standard method).

[0035] The peroxide content was measured using the sodium thiosulfate titration method: a small amount of distilled water was added to a 250 mL volumetric flask, into which 0.1 g of hydrogen peroxide was accurately weighed, with the mass being accurate to 0.001 g; 2 g of potassium iodide and 20 mL of 1:4 sulfuric acid were added, and the solution was placed in a dark place for 10 minutes, and then diluted with 100 mL of distilled water. When the solution turned from dark brown to light yellow, 2 mL of freshly prepared starch solution (10 g / L) was added, and the titration was continued until the solution turned from blue to colorless.

[0036] Note: When residual peroxides are left in the titration reaction, the amount of the substance to be tested should be determined according to the reaction conditions. When measuring the peroxide content in organic matter, first extract an appropriate amount of the organic phase with water and then titrate the aqueous phase.

[0037] Example 2 A continuous production method for oxidized cycloolefins comprises the following steps: At 20°C, 5 g of disodium hydrogen phosphate was mixed with 130 mL of 30% H 2 O 2 Prepare disodium hydrogen phosphate solution by adding 5 g of B 0.5 P 0.5 W 4.5 Mo 4.5 O 31 (C 4 H 12 N) 3 Dissolve in 140 mL of cyclohexene to prepare a catalyst solution of cycloolefin; prepare a quenching agent into a saturated aqueous solution of the quenching agent at 25°C; take an extracting agent for use; wherein the saturated aqueous solution of the quenching agent is a saturated aqueous solution of sodium thiosulfate dissolved in water; The sodium hydrogen phosphate solution and the catalyst of the cycloolefin are respectively introduced into the epoxidation microreactor 5 with an inner diameter of 2.5 mm by metering pumps to complete the epoxidation reaction of the cycloolefin to obtain a reaction product. The epoxidation reaction temperature is 60°C, the pressure is 0.2 MPa, and the reaction time is 1 min. The saturated aqueous solution of the quenching agent is input into the peroxide quenching microreactor 6 by a metering pump and mixed with the reaction product to carry out a peroxide quenching reaction. The quenching agent feed amount is 5.0 mmol / min, the temperature of the oxide quenching reaction is 25°C, the pressure is 0.2 Mpa, and the reaction time is 30 seconds to obtain a reacted material; Subsequently, the reacted material and the extractant are introduced into a centrifugal extractor 7 for centrifugal extraction to obtain an organic phase and an aqueous phase. The aqueous phase is stored in an aqueous phase storage tank 12, and the organic phase is sequentially introduced into an online detection device 8, an organic phase storage tank 9, and a distillation device 10 to finally obtain oxidized cycloolefins and enter an oxidized cycloolefin storage tank 11 for storage; the online detection device 8 analyzes that the content of oxidized cyclohexene in every 100 g of aqueous phase is 1.0 g; during the distillation process of the distillation device 10, the vacuum degree is -10 mbar, the tower bottom temperature is 35°C, and the oxidized cyclohexene is collected at the top of the tower by condensation; the yield of oxidized cyclohexene in this process is 97.9%, the purity is ≥ 99.5%, the peroxide content is 0.95%, and the moisture content is 0.15%; The dosage ratio of the disodium hydrogen phosphate solution to the cycloolefin catalyst solution is 1 g:0.83 g; the dosage ratio of the reaction product to the saturated aqueous solution of the quencher is 1.00 g:0.0064 g.

[0038] Example 3 A continuous production method for oxidized cycloolefins comprises the following steps: At 20°C, 5 g of disodium hydrogen phosphate was mixed with 130 mL of 30% H 2 O 2 Prepare disodium hydrogen phosphate solution by adding 5 g of B 0.5 P 0.5 W 4.5 Mo 4.5 O 31 (C 4 H 12 N) 3 Dissolve in 140 mL of cyclohexene to form a catalyst solution of cycloolefin; prepare a quenching agent into a saturated aqueous solution of the quenching agent at 25°C; take an extracting agent for use; wherein the saturated aqueous solution of the quenching agent is a saturated aqueous solution of sodium bisulfite dissolved in water; The sodium hydrogen phosphate solution and the catalyst of the cycloolefin are respectively introduced into the epoxidation microreactor 5 with an inner diameter of 2.5 mm by metering pumps to complete the epoxidation reaction of the cycloolefin to obtain a reaction product. The epoxidation reaction temperature is 60°C, the pressure is 0.2 MPa, and the reaction time is 1 min. The saturated aqueous solution of the quenching agent is input into the peroxide quenching microreactor 6 by a metering pump and mixed with the reaction product to carry out a peroxide quenching reaction. The quenching agent feed amount is 5.0 mmol / min, the temperature of the oxide quenching reaction is 25°C, the pressure is 0.2 Mpa, and the reaction time is 30 seconds to obtain a reacted material; Subsequently, the reacted material and the extractant are introduced into a centrifugal extractor 7 for centrifugal extraction to obtain an organic phase and an aqueous phase. The aqueous phase is stored in an aqueous phase storage tank 12, and the organic phase is sequentially introduced into an online detection device 8, an organic phase storage tank 9, and a distillation device 10 to finally obtain oxidized cycloolefins and enter an oxidized cycloolefin storage tank 11 for storage; the online detection device 8 analyzes that the content of oxidized cyclohexene in every 100 g of aqueous phase is 1.0 g; during the distillation process of the distillation device 10, the vacuum degree is -10 mbar, the tower bottom temperature is 35°C, and the oxidized cyclohexene is collected at the top of the tower by condensation; the yield of oxidized cyclohexene in this process is 97.9%, the purity is ≥ 99.5%, the peroxide content is 0.95%, and the moisture content is 0.15%; The dosage ratio of the disodium hydrogen phosphate solution to the cycloolefin catalyst solution is 1 g:0.83 g; the dosage ratio of the reaction product to the saturated aqueous solution of the quencher is 1.00 g:0.023 g.

[0039] Example 4 A continuous production method for oxidized cycloolefins comprises the following steps: At 20°C, 5 g of disodium hydrogen phosphate was mixed with 130 mL of 30% H 2 O 2 Prepare disodium hydrogen phosphate solution by adding 5 g of B 0.5 P 0.5 W 4.5 Mo 4.5 O 31 (C 4 H 12 N) 3 Dissolve in 140 mL of cyclohexene to form a catalyst solution of cycloolefin; prepare a quenching agent into a saturated aqueous solution of the quenching agent at 25°C; take an extracting agent for use; wherein the saturated aqueous solution of the quenching agent is a saturated aqueous solution of potassium bisulfite dissolved in water; The sodium hydrogen phosphate solution and the catalyst of the cycloolefin are respectively introduced into the epoxidation microreactor 5 with an inner diameter of 2.5 mm by metering pumps to complete the epoxidation reaction of the cycloolefin to obtain a reaction product. The epoxidation reaction temperature is 60°C, the pressure is 0.2 MPa, and the reaction time is 1 min. The saturated aqueous solution of the quenching agent is input into the peroxide quenching microreactor 6 by a metering pump and mixed with the reaction product to carry out a peroxide quenching reaction. The quenching agent feed amount is 5.0 mmol / min, the temperature of the oxide quenching reaction is 25°C, the pressure is 0.2 Mpa, and the reaction time is 30 seconds to obtain a reacted material; Subsequently, the reacted material and the extractant are introduced into a centrifugal extractor 7 for centrifugal extraction to obtain an organic phase and an aqueous phase. The aqueous phase is stored in an aqueous phase storage tank 12, and the organic phase is sequentially introduced into an online detection device 8, an organic phase storage tank 9, and a distillation device 10 to finally obtain oxidized cycloolefins and enter an oxidized cycloolefin storage tank 11 for storage; the online detection device 8 analyzes that the content of oxidized cyclohexene in every 100 g of aqueous phase is 1.0 g; during the distillation process of the distillation device 10, the vacuum degree is -10 mbar, the tower bottom temperature is 35°C, and the oxidized cyclohexene is collected at the top of the tower by condensation; the yield of oxidized cyclohexene in this process is 97.9%, the purity is ≥ 99.5%, the peroxide content is 0.95%, and the moisture content is 0.15%; The dosage ratio of the disodium hydrogen phosphate solution to the cycloolefin catalyst solution is 1 g:0.83 g; the dosage ratio of the reaction product to the saturated aqueous solution of the quencher is 1.00 g:0.00353 g).

[0040] The reaction material then passed through a phase separator and was monitored and analyzed online by gas chromatography. The material entered a collection tank. The peroxide content of the system and the cyclohexene oxide content per 100 g of the aqueous phase are shown in Table 1. The organic phase was distilled by a distillation device 10 to obtain cyclohexene oxide. The vacuum degree during the distillation process was -10 mbar, and the bottom temperature was 35°C. High-quality cyclohexene oxide was collected at the top of the tower through condensation and entered the cycloolefin oxide storage tank 11. The yield and quality of high-quality cyclohexene oxide are shown in Table 1.

[0041] Table 1: Effects of different quenching agents and quenching reaction time on the yield and quality of cyclohexene oxide

[0042] According to the data in the above table, sodium thiosulfate quenches peroxide, and the chromaticity of the refined product exceeds the standard, while sodium bisulfite and potassium bisulfite quench peroxide, and the various indicators of the refined product meet the standards. Therefore, sodium bisulfite is preferably used as a quencher, and the quenching reaction time is 10s. In the preparation process of the present invention, the oxide quenching reaction is adopted to realize the quenching of the peroxide of the reaction system, which effectively avoids the potential safety hazard caused by peroxide. During the oxide quenching reaction, the addition of the quencher can reduce the solubility of the oxidized cycloolefin in water, and the centrifugal extraction section is used in a supporting manner, which can maximize the recovery of organic matter in the water, improve the product yield, and the extractant can be azeotropic with water, and the moisture content of the oxidized cycloolefin can be significantly reduced in the subsequent distillation section, and the quality of the oxidized cycloolefin is improved, which solves the technical problems of low yield and quality of the oxidized cycloolefin in the prior art.

[0043] Example 5 In container a, 5 g of disodium hydrogen phosphate and 130 mL of 30% H 2 O 2 Prepare solution A by mixing 5 g of B in container b.0.5 P 0.5 W 4.5 Mo 4.5 O 31 (C 4 H 12 N) 3 Dissolve in 140 mL of cyclohexene to prepare solution B, prepare sodium bisulfite into saturated aqueous solution C in container c at 25°C, place different extractants in container d as solution D, and use metering pumps to input solutions A and B into a microchannel with an inner diameter of 2.5 mm, respectively. The feed amount of hydrogen peroxide is 0.5 mol / min, the feed amount of cyclohexene is 0.6 mol / min, the reaction temperature is 60°C, the pressure is 0.2 Mpa, and the reaction time is 1 min. Subsequently, solution C is input into a microchannel with an inner diameter of 2.5 mm using a metering pump, the feed amount of quencher is 5.0 mmol / min, the reaction temperature is 25°C, the pressure is 0.2 Mpa, and the reaction time is 10 seconds. The material, solution D and nitrogen at the outlet of the second microchannel reactor enter the centrifugal extractor 7 for 1-4 level centrifugal extraction, the feed rate of solution D is 2 ml / min, the aqueous phase enters the aqueous phase storage tank 12, and the organic phase enters the organic phase storage tank 9 after online monitoring and analysis by gas chromatography. The peroxide content of the system and the content of cyclohexene oxide per 100 g of aqueous phase are shown in Table 3; 5. The organic phase is distilled to obtain cyclohexene oxide. The vacuum degree during the distillation process is -10 mbar, the tower bottom temperature is 35°C, and the top of the tower is condensed to collect high-quality cyclohexene oxide. The yield and quality of high-quality cyclohexene oxide are shown in the following table.

[0044] Table 2: Effect of reaction temperature in quenching section on yield and quality of cyclohexene oxide

[0045] It can be seen that when the temperature of the quenching reaction section is lower than 25°C, the peroxide content is not completely quenched due to the reaction temperature being too low and the reaction time being too short. Therefore, the preferred reaction time of the quenching reaction section is 10 seconds and the reaction temperature is 25°C.

[0046] Example 6 In container a, 5 g of disodium hydrogen phosphate and 130 mL of 30% H 2 O 2 Prepare solution A by mixing 5 g of B in container b. 0.5 P 0.5 W 4.5 Mo 4.5 O 31 (C 4 H 12 N) 3Dissolve in 140 mL of cyclohexene to prepare solution B, prepare sodium bisulfite into saturated aqueous solution C in container c at 25°C, place different extractants in container d as solution D, and use metering pumps to input solutions A and B into a microchannel with an inner diameter of 2.5 mm, respectively. The feed amount of hydrogen peroxide is 0.5 mol / min, the feed amount of cyclohexene is 0.6 mol / min, the reaction temperature is 60°C, the pressure is 0.2 Mpa, and the reaction time is 1 min. Subsequently, solution C is input into a microchannel with an inner diameter of 2.5 mm using a metering pump, the feed amount of quencher is 5.0 mmol / min, the reaction temperature is 25°C, the pressure is 0.2 Mpa, and the reaction time is 10 seconds. The material, solution D and nitrogen at the outlet of the second microchannel reactor enter the centrifugal extractor for 1-4 stage centrifugal extraction, the feed rate of solution D is 2 ml / min, the aqueous phase enters the aqueous phase storage tank 12, the organic phase enters the organic phase storage tank 9 after online monitoring and analysis by gas chromatography, the peroxide content of the system and the content of cyclohexene oxide per 100 g aqueous phase are shown in Table 3; 5. The organic phase is distilled to obtain cyclohexene oxide, the vacuum degree during the distillation process is -10 mbar, the tower bottom temperature is 35°C, and the top of the tower is condensed to collect high-quality cyclohexene oxide. The yield and quality of high-quality cyclohexene oxide are shown in the following table.

[0047] Different extractants that can azeotropize with water and centrifugal extraction stages have a significant effect on improving the yield and quality of cyclohexene oxide. In order to make the reaction system simpler, no additional organic solvent is used, cyclohexene is selected as the extractant, and two-stage centrifugal extraction is used as the optimal operating condition of the centrifugal extraction section.

[0048] Table 3: Effects of different extractants and extraction stages on the yield and quality of cyclohexene oxide

[0049] Example 7 In container a, 5 g of disodium hydrogen phosphate and 130 mL of 30% H 2 O 2Solution A was prepared, 5 g of catalyst was dissolved in 140 mL of cyclohexene in container b to prepare solution B, sodium bisulfite was prepared into saturated aqueous solution C at 25°C in container c, cyclohexene was placed in container d as solution D, solutions A and B were respectively input into a microchannel with an inner diameter of 2.5 mm using a metering pump, the feed amount of hydrogen peroxide was 0.5 mol / min, the feed amount of cyclohexene was 0.6 mol / min, the reaction temperature was 60°C, the pressure was 0.2 Mpa, and the reaction time was 1 min. Subsequently, solution C was input into a microchannel with an inner diameter of 2.5 mm using a metering pump, the feed amount of sodium bisulfite was 5.0 mmol / min, the reaction temperature was 25°C, the pressure was 0.2 Mpa, and the reaction time was 10 seconds. The material, solution D and nitrogen at the outlet of the second microchannel reactor enter the centrifugal extractor for secondary centrifugal extraction. The feed rate of solution D is 2 ml / min. The aqueous phase enters the aqueous phase storage tank 12. The organic phase enters the organic phase storage tank 9 after online monitoring and analysis by gas chromatography. No peroxide is detected in the system; 5. The organic phase is distilled to obtain cyclohexene oxide. The vacuum degree during the distillation process is -10 mbar, the bottom temperature is 35°C, and high-quality cyclohexene oxide is collected at the top of the tower by condensation; the yield and quality of high-quality cyclohexene oxide are shown in the table below.

[0050] Table 4: Effect of different catalysts on the yield and quality of cyclohexene oxide

[0051] Different catalysts that can be dissolved in cyclohexene were studied. The catalytic efficiency of different catalysts in the epoxidation reaction section, which led to differences in the yield of oxidized cyclohexene, was not affected. This proved that the process stability of the peroxide quenching section, centrifugal extraction section and refining section of the present invention is extremely good.

[0052] Example 8 In container a, 5 g of disodium hydrogen phosphate and 130 mL of 30% H 2 O 2Solution A was prepared, 5 g of the catalyst was dissolved in 140 mL of cyclopentene in container b to prepare solution B, sodium bisulfite was prepared into a saturated aqueous solution C at 25°C in container c, cyclopentene was placed in container d as solution D, solutions A and B were respectively input into a microchannel with an inner diameter of 2.5 mm using a metering pump, the feed amount of hydrogen peroxide was 0.5 mol / min, the feed amount of cyclopentene was 0.6 mol / min, the reaction temperature was 60°C, the pressure was 0.2 Mpa, and the reaction time was 1 min. Subsequently, solution C was input into a microchannel with an inner diameter of 2.5 mm using a metering pump, the feed amount of sodium bisulfite was 5.0 mmol / min, the reaction temperature was 25°C, the pressure was 0.2 Mpa, and the reaction time was 10 seconds. The material, solution D and nitrogen at the outlet of the second microchannel reactor enter the centrifugal extractor for 2-stage centrifugal extraction. The feed rate of solution D is 2 ml / min. The aqueous phase enters the aqueous phase storage tank 12. The organic phase enters the organic phase storage tank 9 after online monitoring and analysis by gas chromatography. The peroxide content of the system is 0%. 5. The organic phase is distilled to obtain cyclopentene oxide. The vacuum degree during the distillation process is -10 mbar, the tower bottom temperature is 35°C, and the top of the tower is condensed to collect high-quality cyclopentene oxide. The yield of cyclopentene oxide is 98.2%, the purity is ≥99.5%, and the water content is 0.03%.

[0053] Example 9 In container a, 5 g of disodium hydrogen phosphate and 130 mL of 30% H 2 O 2 Solution A was prepared, 5 g of the catalyst was dissolved in 140 mL of limonene in container b to prepare solution B, sodium bisulfite was prepared into a saturated aqueous solution C at 25°C in container c, dichloroethane was placed in container d as solution D, solutions A and B were respectively input into a microchannel with an inner diameter of 2.5 mm using a metering pump, the feed amount of hydrogen peroxide was 0.5 mol / min, the feed amount of limonene was 0.6 mol / min, the reaction temperature was 60°C, the pressure was 0.2 Mpa, and the reaction time was 1 min. Subsequently, solution C was input into a microchannel with an inner diameter of 2.5 mm using a metering pump, the feed amount of sodium bisulfite was 5.0 mmol / min, the reaction temperature was 25°C, the pressure was 0.2 Mpa, and the reaction time was 10 seconds. The material, solution D and nitrogen at the outlet of the second microchannel reactor enter the centrifugal extractor for 3-stage centrifugal extraction. The feed rate of solution D is 3 ml / min. The aqueous phase enters the aqueous phase storage tank 12, and the organic phase enters the organic phase storage tank 9 after online monitoring and analysis by gas chromatography; 5. The organic phase is distilled to obtain oxidized limonene. The vacuum degree during the distillation process is -10 mbar, the tower bottom temperature is 70°C, and the high-quality oxidized limonene is collected by condensation at the top of the tower. The yield of oxidized limonene is 97.9%, the purity is ≥ 99.7%, the peroxide content is 0%, and the moisture content is 0.01%.

[0054] The above contents are only for explaining the technical idea of ​​the present invention and cannot be used to limit the protection scope of the present invention. Any changes made on the basis of the technical solution in accordance with the technical idea proposed by the present invention shall fall within the protection scope of the claims of the present invention.

Claims

1. A continuous production method of oxidized cycloolefins, characterized in that: The following steps are involved: After mixing the disodium hydrogen phosphate solution and the catalyst solution of the cycloolefin, an epoxidation reaction is carried out to obtain a reaction product; After mixing the reaction product and a saturated aqueous solution of a quenching agent, a peroxide quenching reaction is performed to obtain a post-reaction material; The obtained reaction material is subjected to centrifugal extraction to obtain an organic phase and an aqueous phase. The organic phase is subjected to rectification to obtain oxidized cycloolefins.

2. The continuous production method of an oxidized cycloolefin according to claim 1, characterized in that: The epoxidation reaction temperature is 25-35°C, and the reaction time is 1.0-2.0 min; The temperature of the oxide quenching reaction is 25-35° C., and the reaction time is 10-30 seconds.

3. The continuous production method of an oxidized cycloolefin according to claim 1, characterized in that: The vacuum degree of the distillation is -10~-15mbar, and the temperature is 35-70℃.

4. The continuous production method of an oxidized cycloolefin according to claim 1, characterized in that: The dosage ratio of the disodium hydrogen phosphate solution and the cycloolefin catalyst solution is 1 g: (0.83-1) g; The disodium hydrogen phosphate solution is obtained by mixing disodium hydrogen phosphate and hydrogen peroxide; the concentration of the disodium hydrogen phosphate solution is 3.85-4.5 g / mL; the cycloolefin catalyst solution is obtained by dissolving the catalyst in the cycloolefin; the concentration of the cycloolefin catalyst solution is 3.57-4.5 g / mL; The mass ratio of the reaction product to the saturated aqueous solution of the quencher is 1.00 g: ((0.003-0.03) g); The saturated aqueous solution of the quenching agent is one of sodium thiosulfate, sodium bisulfite and potassium bisulfite.

5. The method for continuous production of oxidized cycloolefins according to claim 4, characterized in that: The cycloolefin is one of cyclohexene, cyclopentene and limonene; the catalyst is a boron-phosphorus-doped tungsten-molybdenum catalyst; The boron-phosphorus doped tungsten-molybdenum catalyst is: (C4H 12 N)3BPW 4.5 You 4.5 Or 30 、(C 16 H 36 N)3BPW 4.5 You 4.5 Or 30 、 (C 22 H 48 N)3BPW 4.5 You 4.5 Or 30 ,(C 38 H 80 N)3BPW 4.5 You 4.5 Or 30 、 (C 11 H 26 N)3BPW 4.5 You 4.5 Or 30 、(C 13 H 30 N)3BPW 4.5 You 4.5 Or 30 、 (C 21 H 46 N)3BPW 4.5 Mo 4.5 O 30 and (C 19 H 42 N)3BPW 4.5 Mo 4.5 O 30 One or more of .

6. The continuous production of an oxidized cycloolefin according to claim 1, characterized in that: The centrifugal extraction is carried out after mixing the reaction material and the extractant, and the feed amount of the extractant is 2-3 mL / min; the extractant is one or more of ethylene dichloride, ethyl acetate, raw material cyclic olefin, benzene, cyclohexane and toluene.

7. A continuous production system for oxidized cycloolefins, characterized in that: It comprises an epoxidation reaction raw material supply system (1), a peroxide quenching reaction raw material supply system (2), a centrifugal extraction raw material supply system (3), an epoxidation reaction module, a peroxide quenching reaction module, a centrifugal extraction module and a product collection module; The epoxidation reaction raw material supply system (1) is connected to the inlet of the epoxidation reaction module; the outlet of the epoxidation reaction module is connected to the inlet of the peroxide quenching reaction module; the outlet of the peroxide quenching reaction module is connected to the centrifugal extraction module; and the outlet of the centrifugal extraction module is connected to the product collection module; The peroxide quenching reaction raw material supply system (2) is connected to the inlet of the peroxide quenching reaction module; and the centrifugal extraction raw material supply system (3) is connected to the inlet of the centrifugal extraction module.

8. The continuous production system of oxidized cycloolefin according to claim 7, characterized in that: The epoxidation reaction module is an epoxidation microreactor (5); the peroxide quenching reaction module is a peroxide quenching microreactor (6); and the centrifugal extraction module is a centrifugal extractor (7); The epoxidation reaction raw material supply system (1) is connected to the inlet of the epoxidation microreactor (5); and a micro mixer (4) is connected between the epoxidation reaction raw material supply system (1) and the inlet of the epoxidation microreactor (5).

9. A continuous production system of oxidized cycloolefins according to claim 8, characterized in that: The product collection module includes an organic phase collection system and an aqueous phase collection system; The organic phase outlet of the centrifugal extractor (7) is connected to the organic phase collection system; the water phase outlet of the centrifugal extractor (7) is connected to the water phase collection system; The organic phase collection system comprises an online detection device (8), an organic phase storage tank (9), a distillation device (10) and an oxidized cycloolefin storage tank (11); the aqueous phase collection system is an aqueous phase storage tank (12); The organic phase outlet of the centrifugal extractor (7) is connected in sequence to the line detection device (8), the organic phase storage tank (9), the distillation device (10) and the oxidized cycloolefin storage tank (11); The water phase outlet of the centrifugal extractor (7) is connected to the water phase storage tank (12).

10. Use of the continuous production system of oxidized cycloolefins according to any one of claims 7 to 9, characterized in that: The continuous production system of oxidized cycloolefins is used to implement the production method described in any one of claims 1 to 6.

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