CN110684005A - Cyclic injection type continuous reaction process for preparing cyclic carbonate - Google Patents

Abstract

The invention provides a cyclic spray type continuous reaction process for preparing cyclic carbonate, belonging to the technical field of cyclic carbonate preparation. The process adopts a circulating jet reactor, uses an "electrophilic-nucleophilic" bifunctional system as a catalyst, and conducts coupling with carbon dioxide and alkylene oxide as raw materials at a reaction pressure of 0.4-5.0 MPa and a reaction temperature of 25-180 °C The reaction continuously produces cyclic carbonates. Compared with the existing circulating jet batch reaction process, the continuous process proposed by the invention has the advantages of high production efficiency, stable and controllable reaction and stable quality parameters of the product.

Description

A kind of circulating spray type continuous reaction process for preparing cyclic carbonate

technical field

The invention belongs to the technical field of cyclic carbonate preparation, and relates to a cyclic spray type continuous reaction process for preparing cyclic carbonate by using alkylene oxide and carbon dioxide as raw materials.

Background technique

Carbon dioxide (CO ₂ ), as an important carbon source on the earth, can be converted into carbohydrates through photosynthesis, and oxygen is released at the same time, which is one of the most important reactions to maintain ecological cycles. However, the excessive emission of CO ₂ in human daily life and industrial production has disrupted the "balance of payments" in nature, making CO ₂ the main gas that causes the greenhouse effect. Therefore, the abatement and chemical or physical fixation of _CO2 has become one of the most important strategic research topics worldwide. Under the action of catalyst, carbon dioxide can react with alkylene oxide to prepare cyclic carbonate. As high-boiling, high-polarity organic solvents with excellent properties, these cyclic carbonates are widely used in organic synthesis, cosmetic industry, gas separation, battery electrolyte and metal extraction.

At present, there are many patent reports at home and abroad on the preparation of cyclic carbonate by coupling carbon dioxide and alkylene oxide. For example, in US 4314945, McMullen used tetrahydrocarbyl quaternary ammonium salt to catalyze the reaction of alkylene oxide with carbon dioxide to synthesize cyclic carbonate; in US 4786741 and US 4841072, Sachs and Harvey used quaternary phosphonium salt catalysts respectively under the pressure of 2.5-20MPa , realized the cycloaddition reaction of carbon dioxide and ethylene oxide, and prepared the corresponding cyclic carbonate; in US 4931571, Weinstein used quaternary arsine halide as a catalyst to catalyze carbon dioxide and ethylene oxide at 90 ~ 200 ℃ alkane reaction to synthesize ethylene carbonate. Some domestic experts have also made some breakthroughs in this field. For example, in CN1343668, Deng Youquan used ionic liquid and alkali metal halide or tetrabutylammonium bromide to form a binary catalytic system. At 1.5-4.5MPa, the epoxy compound was successfully converted into the corresponding cyclic carbonate; in CN 101003531, He Liangnian used polyethylene glycol functionalized with quaternary ammonium salt or quaternary phosphonium salt as a catalyst to realize carbon dioxide. The corresponding cyclic carbonates were synthesized by coupling reaction with alkylene oxides. The advantage of the catalyst is that it is easy to recover and recycle, and is suitable for continuous production; in CN 101972674, Liu Binyuan synthesized a simple tetradentate Schiff base aluminum complex containing quaternary ammonium salt in the molecule, and the catalyst is used for catalysis In the coupling reaction of carbon dioxide and alkylene oxide, the catalytic efficiency can reach up to 3750 mol cyclic carbonate/mol catalyst. In recent years, we have also used tetradentate Schiff base aluminum complexes as catalysts. Under the synergistic effect of quaternary ammonium salts or quaternary phosphonium salts, we have realized the coupling reaction of carbon dioxide and alkylene oxide, and synthesized the corresponding cyclic carbonate ( CN 1416953, CN 1415416 and CN 1544431).

In the methods for preparing cyclic carbonates reported above, traditional still-type or shell-and-tube reaction processes have been adopted. In these processes, when the conversion of alkylene oxide reaches a certain level, the reaction rate shows a sharp drop, resulting in a long time required to achieve almost complete conversion of alkylene oxide. Therefore, the kettle type or tubular type reaction process has low efficiency and high energy consumption. In CN 110003163 A, we adopted the circulating jet reaction method to replace the traditional kettle type or shell-and-tube reaction process, and realized the efficient reaction of carbon dioxide and alkylene oxide, but this method is a batch reaction process, and the efficiency needs to be further improved.

SUMMARY OF THE INVENTION

The invention provides a cyclic injection continuous reaction process for preparing epoxy carbonate by using carbon dioxide and alkylene oxide as raw materials.

Technical scheme of the present invention:

A cyclic injection type continuous reaction process for preparing cyclic carbonate adopts a cyclic injection reactor, uses an "electrophilic-nucleophilic" bifunctional system as a catalyst, and reacts at a reaction pressure of 0.4-5.0 MPa and a temperature of 25-180 °C At the same temperature, carbon dioxide and alkylene oxide are used as raw materials for coupling reaction to continuously prepare cyclic carbonate.

The reaction process is as follows: adding a certain amount of cyclic carbonate containing a catalyst into the circulating jet reactor, heating the starting material to the reaction temperature through a heat exchanger, and feeding carbon dioxide to the reaction pressure; continuously adding cyclic carbonate to the circulating jet reactor Oxyalkane and cyclic carbonate dissolved with catalyst, and carbon dioxide is added to keep the reaction pressure constant; after the material level in the circulating jet reactor reaches the set value, the reaction material begins to transfer to the aging tank, and the material in the aging tank is to be After the liquid level rises to a certain height and ensures that the conversion rate of alkylene oxide reaches 99.9%, the reaction material starts to be transferred to the flash tank, carbon dioxide is discharged, and vacuum distillation is performed to obtain cyclic carbonate, and the residual liquid containing the catalyst is recycled; all In the process, it is necessary to control the balance of material in and out of the circulating jet reactor, aging tank, and flash tank to maintain a stable state of continuous feeding reaction and discharging collection;

The general formula of the "electrophilic" part of the "electrophilic-nucleophilic" bifunctional catalyst is M ¹ _a [M ² (CN) _b L ¹ _c ] _d · x [M ³ _m X _n ] · y L ² ·z H ₂ O. In the formula, M ¹ and M ³ are selected from Zn ²⁺ , Co ²⁺ , Ni ²⁺ , Fe ²⁺ , Fe ³⁺ , Ca ²⁺ , Mg ²⁺ , Cu ²⁺ , Cr ³⁺ , Al ³⁺ , Sn ²⁺ , Cd ²⁺ or Pb ²⁺ , preferably Zn ²⁺ , Co ²⁺ , Ni ²⁺ , Fe ²⁺ , Fe ³⁺ ; M ² is selected from Co ³⁺ , Ni ²⁺ , Fe ²⁺ , Fe ³⁺ , Cr ³⁺ , Mn ³⁺ or Cu ²⁺ ; L ¹ is an internal ligand coordinating with M ² , selected from monodentate or polydentate composed of C, H, N, O, P and S Ligand; X is F ^- , Cl ^- , Br ^- , I ^- , NO ₃ ^- , CH ₃ COO ^- , SO ₄ ^2- , methylbenzoate, p-toluenesulfonate, o-nitrophenoloxy , p-nitrophenol oxygen, m-nitrophenol oxygen and other aryloxy anions or organic carboxylate anions; L is selected from water ^- soluble heteroatom organic complexing agents, such as: alcohols, aldehydes, ketones, ethers, esters, Amides, ureas, nitriles, sulfides or mixtures thereof, preferably tert-butanol, isopropanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, dimethoxyethane and tert-amyl alcohol; a, b, d , m and n are zero or the values satisfy the balance of positive and negative charges, where b is a positive integer; x is a positive number, and c, y and z are zero or positive. The general formula of the "nucleophilic" moiety is a salt of R ¹ R ² ₃ YX ¹ , wherein: R ¹ is C ₁ -C ₁₆ alkyl, R ² is C ₁ -C ₆ alkyl or phenyl; Y is nitrogen , phosphorus or arsenic; X ¹ is Cl ^-1 , Br ^-1 , I ^-1 , NO ₃ ^-1 , CH ₃ COO ^-1 , ClO ₄ ^-1 , BF ₄ ^-1 , OH ^-1 , BPh ₄ ^-1 Or N ₃ ^-1 monovalent anion. The mass ratio of the "electrophilic" moiety to the "nucleophilic" moiety is 1:1 to 1:50.

The mass ratio of the alkylene oxide to the catalyst is 5:1 to 50000:1, preferably 100:1 to 500:1.

The mass ratio of alkylene oxide and cyclic carbonate in the catalyst-dissolved mixed solution is 1:20-20:1, preferably 1:2-2:1;

The alkylene oxide is ethylene oxide or propylene oxide.

Beneficial effects of the present invention:

(1) The existing batch reaction method is changed, which can be carried out continuously and efficiently, and greatly improves the industrial production efficiency.

(2) The reaction is stable and controllable, and the quality parameters of the product are stable.

Description of drawings

Fig. 1 is the process flow diagram of the continuous catalyzed preparation of cyclic carbonate by circulating spray type gas-liquid contact.

Detailed ways

Example 1: 4.0Kg propylene carbonate containing 270g "electrophilic-nucleophilic" bifunctional catalyst was added to a circulating jet reactor with an effective volume of 20L, wherein the "electrophilic" moiety was Zn ₃ [Fe(CN) ₅ ] PPh ₃ ] ₂ ·2.8[ZnCl ₂ ]·2 ^t BuOH0.9H ₂ O, the "nucleophilic" part is tetrabutylammonium bromide, and the mass ratio of the two is 1:1. The reaction device was started, and the starting material was heated to 25° C. through a heat exchanger, and carbon dioxide was introduced into the reaction system until the pressure was 0.4 MPa. The aging tank was heated to 25°C through a heat exchanger, and carbon dioxide was introduced to the aging tank until the pressure was 0.2 MPa. Prepare a mixed solution of propylene carbonate and the above-mentioned "electrophilic-nucleophilic" bifunctional catalyst with a mass ratio of 5:1, add propylene oxide at a rate of 3.0Kg/h, and add catalyst-containing propylene carbonate at a rate of 3.6Kg/h to mix liquid, the mass ratio of propylene oxide and propylene carbonate is controlled to be 1:1, carbon dioxide is continuously supplemented (the speed is maintained at 2.1-2.3Kg/h), and the pressure of the control system is maintained at 0.4MPa. During the feeding process, the material in the reactor is controlled by the interlocking of the liquid level gauge and the solenoid valve to maintain 4Kg, and the material growing at the bottom of the jet reactor is pressed into the aging tank. Complete all reactions. As the material is added, the liquid level in the aging tank gradually increases. The material in the aging tank is controlled to be maintained at 8.9Kg through the interlocking of the aging tank level gauge and the solenoid valve, and carbon dioxide is used as the pressure supplement to maintain the aging tank pressure of 0.2MPa. The aged material is transferred to a flash tank, and after carbon dioxide is discharged, it is distilled under reduced pressure. Under this equilibrium, the aging time of the material in the aging tank is about 60 minutes, and the conversion rate of alkylene oxide reaches 99.9%. After continuous operation for 12h, about 63.3Kg of propylene carbonate (selectivity>99.5%) was obtained, and the remaining 43.2Kg of catalyst-containing propylene carbonate residue was recycled for use. This method can realize an annual output of 46 tons of propylene carbonate in a 20L circulating spray device.

Example 2: 4.0Kg propylene carbonate containing 10g "electrophilic-nucleophilic" bifunctional catalyst was added to a circulating jet reactor with an effective volume of 20L, wherein the "electrophilic" moiety was Zn ₃ [Fe(CN) ₅ PPh ₃ ] ₂ ·2.8[ZnCl ₂ ]·2 ^t BuOH0.9H ₂ O, the "nucleophilic" part is tetrabutylammonium bromide, and the mass ratio of the two is 1:5. The reaction device was started, and the starting material was heated to 110° C. through a heat exchanger, and carbon dioxide was introduced into the reaction system until the pressure was 2.0 MPa. The aging tank was heated to 110° C. through a heat exchanger, and carbon dioxide was introduced until the pressure of the aging tank was 1.8 MPa. Prepare a mixed solution of propylene carbonate and the above-mentioned "electrophilic-nucleophilic" bifunctional catalyst with a mass ratio of 150:1, add propylene oxide at a rate of 9.1Kg/h, and add catalyst-containing propylene carbonate at a rate of 9.1Kg/h to mix liquid, the mass ratio of propylene oxide and propylene carbonate is controlled to be 1:1, carbon dioxide is continuously supplemented (the speed is maintained at 6.6-6.9Kg/h), and the pressure of the control system is maintained at 2.0MPa. During the feeding process, the material in the reactor is controlled by the interlocking of the liquid level gauge and the solenoid valve to maintain 4Kg, and the material growing at the bottom of the jet reactor is pressed into the aging tank. Complete all reactions. As the material is added, the liquid level in the aging tank gradually increases. The material in the aging tank is controlled to be maintained at 12.5Kg through the interlocking of the aging tank level gauge and the solenoid valve, and carbon dioxide is used as pressure supplement to maintain the aging tank pressure of 1.8MPa. The aged material is transferred to a flash tank, and after carbon dioxide is discharged, it is distilled under reduced pressure. Under this equilibrium, the aging time of the material in the aging tank is about 30 minutes, and the conversion rate of alkylene oxide reaches 99.9%. After continuous operation for 12h, about 192.0Kg of propylene carbonate (selectivity>99.5%) was obtained, and the remaining 109.2Kg of catalyst-containing propylene carbonate residue was recycled for use. This method can realize an annual output of 140 tons of propylene carbonate in a 20L circulating spray device.

Example 3: 4.0Kg of propylene carbonate containing 5g of "electrophilic-nucleophilic" bifunctional catalyst was added to a circulating jet reactor with an effective volume of 20L, wherein the "electrophilic" moiety was Zn ₃ [Co(CN) ₃ ( PPh ₃ ) ₃ ] ₂ ·1.8[ZnCl ₂ ]·2CH ₃ OH0.9H ₂ O, the "nucleophilic" part is tetrabutylammonium bromide, and the mass ratio of the two is 1:50. The reaction device was started, and the starting material was heated to 180° C. through a heat exchanger, and carbon dioxide was introduced into the reaction system until the pressure was 5.0 MPa. The aging tank was heated to 180 ℃ through a heat exchanger, and carbon dioxide was introduced to the aging tank until the pressure was 4.8 MPa. Prepare a mixed solution of propylene carbonate and the above-mentioned "electrophilic-nucleophilic" bifunctional catalyst with a mass ratio of 300:1, add propylene oxide at a rate of 9.1Kg/h, and add catalyst-containing propylene carbonate at a rate of 9.1Kg/h to mix liquid, the mass ratio of propylene oxide and propylene carbonate is controlled to be 1:1, carbon dioxide is continuously supplemented (the speed is maintained at 6.6-6.9Kg/h), and the pressure of the control system is maintained at 5.0MPa. During the feeding process, the material in the reactor is controlled by the interlocking of the liquid level gauge and the solenoid valve to maintain 4Kg, and the material growing at the bottom of the jet reactor is pressed into the aging tank. Complete all reactions. As the material is added, the liquid level in the aging tank gradually increases. The material in the aging tank is controlled to be maintained at 8.4Kg through the interlocking of the aging tank level gauge and the solenoid valve, and carbon dioxide is used as pressure supplement to maintain the aging tank pressure of 4.8MPa. The aged material is transferred to a flash tank, and after carbon dioxide is discharged, it is distilled under reduced pressure. Under this equilibrium, the aging time of the material in the aging tank is about 20 minutes, and the conversion rate of alkylene oxide reaches 99.9%. After continuous operation for 12h, about 192.0Kg of propylene carbonate (selectivity>99.5%) was obtained, and the remaining 109.2Kg of catalyst-containing propylene carbonate residue was recycled for use. This method can realize an annual output of 140 tons of propylene carbonate in a 20L circulating spray device.

Example 4: Addition of 4.0Kg propylene carbonate containing 10g "electrophilic-nucleophilic" bifunctional catalyst in a circulating jet reactor with an effective volume of 20L, wherein the "electrophilic" moiety is Zn ₃ [Fe(CN) ₅ PPh ₃ ] ₂ ·2.8[ZnCl ₂ ]·2 ^t BuOH0.9H ₂ O, the "nucleophilic" part is tetrabutylammonium bromide, and the mass ratio of the two is 1:5. The reaction device was started, and the starting material was heated to 110° C. through a heat exchanger, and carbon dioxide was introduced into the reaction system until the pressure was 2.0 MPa. The aging tank was heated to 110° C. through a heat exchanger, and carbon dioxide was introduced until the pressure of the aging tank was 1.8 MPa. Prepare a mixed solution of propylene carbonate and the above-mentioned "electrophilic-nucleophilic" bifunctional catalyst with a mass ratio of 400:1, add propylene oxide at a speed of 1.2Kg/h, and add a mixed solution of propylene carbonate containing catalyst at a speed of 24Kg/h , the mass ratio of propylene oxide and propylene carbonate is controlled to be 1:20, carbon dioxide is continuously supplemented (the speed is maintained at 0.8-0.9Kg/h), and the pressure of the control system is maintained at 2.0MPa. During the feeding process, the material in the reactor is controlled by the interlocking of the liquid level gauge and the solenoid valve to maintain 4Kg, and the material growing at the bottom of the jet reactor is pressed into the aging tank. Complete all reactions. As the material is added, the liquid level in the aging tank gradually increases. The material in the aging tank is controlled to be maintained at 8.7Kg through the interlocking of the aging tank level gauge and the solenoid valve, and carbon dioxide is used as pressure supplement to maintain the aging tank pressure of 1.8MPa. The aged material is transferred to a flash tank, and after carbon dioxide is discharged, it is distilled under reduced pressure. Under this equilibrium, the aging time of the material in the aging tank is about 20 minutes, and the conversion rate of alkylene oxide reaches 99.9%. After continuous operation for 12h, about 25.3Kg of propylene carbonate (selectivity>99.5%) was obtained, and the remaining 288Kg of catalyst-containing propylene carbonate residue was recycled for use. This method can realize an annual output of 18 tons of propylene carbonate in a 20L circulating spray device.

Example 5: Addition of 4.0Kg propylene carbonate containing 5.5g of "electrophilic-nucleophilic" bifunctional catalyst in a circulating jet reactor with an effective volume of 20L, wherein the "electrophilic" moiety is Zn3[Fe(CN _{) 5} PPh ₃ ] ₂ ·2.8[ZnCl ₂ ]·2 ^t BuOH0.9 H ₂ O, the "nucleophilic" part is tetrabutylammonium bromide, and the mass ratio of the two is 1:5. The reaction device was started, and the starting material was heated to 110° C. through a heat exchanger, and carbon dioxide was introduced into the reaction system until the pressure was 2.0 MPa. The aging tank was heated to 110° C. through a heat exchanger, and carbon dioxide was introduced until the pressure of the aging tank was 1.8 MPa. Prepare a mixed solution of propylene carbonate and the above-mentioned "electrophilic-nucleophilic" bifunctional catalyst with a mass ratio of 20:1, add propylene oxide at a rate of 4.0Kg/h, and add catalyst-containing propylene carbonate at a rate of 0.21Kg/h to mix liquid, the mass ratio of propylene oxide and propylene carbonate is controlled to be 20:1, carbon dioxide is continuously supplemented (the speed is maintained at 2.8-3.0Kg/h), and the pressure of the control system is maintained at 2.0MPa. During the feeding process, the material in the reactor is controlled by the interlocking of the liquid level gauge and the solenoid valve to maintain 4Kg, and the material growing at the bottom of the jet reactor is pressed into the aging tank. Complete all reactions. As the material is added, the liquid level in the aging tank gradually increases. The material in the aging tank is controlled to be maintained at 7.2Kg through the interlocking of the aging tank level gauge and the solenoid valve, and carbon dioxide is used as the pressure supplement to maintain the aging tank pressure of 1.8MPa. The aged material is transferred to a flash tank, and after carbon dioxide is discharged, it is distilled under reduced pressure. Under this equilibrium, the aging time of the material in the aging tank is about 60 minutes, and the conversion rate of alkylene oxide reaches 99.9%. After continuous operation for 12 hours, about 84.4Kg of propylene carbonate (selectivity>99.5%) was obtained, and the remaining 2.5Kg of propylene carbonate residue containing catalyst was recycled for use. This method can realize an annual output of 61 tons of propylene carbonate in a 20L circulating spray device.

Example 6: Addition of 4.0Kg propylene carbonate containing 22g "electrophilic-nucleophilic" bifunctional catalyst in a circulating jet reactor with an effective volume of 20L, where the "electrophilic" moiety is Zn3[Fe(CN _{) 5PPh 3} ] ₂ ·2.8[ZnCl ₂ ]·2 ^t BuOH0.9H ₂ O, the "nucleophilic" part is tetrabutylammonium bromide, and the mass ratio of the two is 1:5. The reaction device was started, and the starting material was heated to 110° C. through a heat exchanger, and carbon dioxide was introduced into the reaction system until the pressure was 2.0 MPa. The aging tank was heated to 110° C. through a heat exchanger, and carbon dioxide was introduced until the pressure of the aging tank was 1.8 MPa. Prepare a mixed solution of propylene carbonate and the above-mentioned "electrophilic-nucleophilic" bifunctional catalyst with a mass ratio of 5:1, add propylene oxide at a rate of 8.0Kg/h, and add catalyst-containing propylene carbonate at a rate of 0.48Kg/h to mix liquid, the mass ratio of propylene oxide and propylene carbonate is controlled to be 20:1, carbon dioxide is continuously supplemented (the speed is maintained at 5.8-6.1Kg/h), and the pressure of the control system is maintained at 2.0MPa. During the feeding process, the material in the reactor is controlled by the interlocking of the liquid level gauge and the solenoid valve to maintain 4Kg, and the material growing at the bottom of the jet reactor is pressed into the aging tank. Complete all reactions. As the material is added, the liquid level in the aging tank gradually increases. The material in the aging tank is controlled to be maintained at 9.7Kg through the interlocking of the aging tank level gauge and the solenoid valve, and carbon dioxide is used as the pressure supplement to maintain the aging tank pressure of 1.8MPa. The aged material is transferred to a flash tank, and after carbon dioxide is discharged, it is distilled under reduced pressure. Under this equilibrium, the aging time of the material in the aging tank is about 40 minutes, and the conversion rate of alkylene oxide reaches 99.9%. After continuous operation for 12h, about 168.8Kg of propylene carbonate (selectivity>99.5%) was obtained, and the remaining 5.8Kg of catalyst-containing propylene carbonate residue was recycled for use. This method can realize an annual output of 123 tons of propylene carbonate in a 20L circulating spray device.

Example 7: Addition of 4.0Kg ethylene carbonate containing 10g "electrophilic-nucleophilic" bifunctional catalyst in a circulating jet reactor with an effective volume of 20L, wherein the "electrophilic" moiety is Zn ₃ [Fe(CN) ₆ ] ₂ ·2.1[ZnCl ₂ ]·1.8 ^t BuOH1.2H ₂ O, the "nucleophilic" part is tetrabutylammonium iodide, and the mass ratio of the two is 1:2. The reaction device was started, and the starting material was heated to 45° C. through a heat exchanger, and carbon dioxide was introduced into the reaction system until the pressure was 0.4 MPa. The aging tank was heated to 45°C through a heat exchanger, and carbon dioxide was introduced to the aging tank until the pressure was 0.2 MPa. Prepare a mixed solution of ethylene carbonate and the above-mentioned "electrophilic-nucleophilic" bifunctional catalyst with a mass ratio of 10:1, add ethylene oxide at a speed of 4.0Kg/h, and add catalyst-containing ethylene carbonate at a speed of 4.4Kg/h Mixed liquid (to be maintained above 40°C), control the mass ratio of ethylene oxide to ethylene carbonate to 1:1, continue to supplement carbon dioxide (the speed is maintained at 3.8-4.0Kg/h), and the control system pressure is maintained at 0.4MPa. During the feeding process, the material in the reactor is controlled by the interlocking of the liquid level gauge and the solenoid valve to maintain 4Kg, and the material growing at the bottom of the jet reactor is pressed into the aging tank. Complete all reactions. As the material is added, the liquid level in the aging tank gradually rises. The material in the aging tank is controlled to be maintained at 12.4Kg through the interlocking of the aging tank level gauge and the solenoid valve, and carbon dioxide is used as a pressure supplement to maintain the aging tank pressure of 0.2MPa. The aged material is transferred to a flash tank, and after carbon dioxide is discharged, it is distilled under reduced pressure. Under this equilibrium, the aging time of the material in the aging tank is about 60 minutes, and the conversion rate of alkylene oxide reaches 99.9%. After continuous operation for 12h, about 96Kg of ethylene carbonate (selectivity>99.5%) was obtained, and the remaining 52.8Kg of ethylene carbonate residue containing catalyst was recycled for use. This method can realize an annual output of 70 tons of ethylene carbonate in a 20L circulating spray device.

Example 8: Addition of 4.0Kg ethylene carbonate containing 13g "electrophilic-nucleophilic" bifunctional catalyst in a circulating jet reactor with an effective volume of 20L, where the "electrophilic" moiety is Zn ₃ [Fe(CN) ₆ ] ₂ ·2.1[ZnCl ₂ ]·1.8 ^t BuOH1.2H ₂ O, the "nucleophilic" part is tetrabutylammonium iodide, and the mass ratio of the two is 1:2. The reaction device was started, and the starting material was heated to 110° C. through a heat exchanger, and carbon dioxide was introduced into the reaction system until the pressure was 2.0 MPa. The aging tank was heated to 110° C. through a heat exchanger, and carbon dioxide was introduced until the pressure of the aging tank was 1.8 MPa. Prepare a mixed solution of ethylene carbonate and the above-mentioned "electrophilic-nucleophilic" bifunctional catalyst with a mass ratio of 100:1, add ethylene oxide at a speed of 8.0Kg/h, and add catalyst-containing ethylene carbonate at a speed of 8.0Kg/h Mixed solution (maintain above 40℃), control the mass ratio of ethylene oxide and ethylene carbonate to 1:1, continue to supplement carbon dioxide (the speed is maintained at 7.8-8.0Kg/h), and control the system pressure to maintain at 2.0MPa. During the feeding process, the material in the reactor is controlled by the interlocking of the liquid level gauge and the solenoid valve to maintain 4Kg, and the material growing at the bottom of the jet reactor is pressed into the aging tank. Complete all reactions. As the material is added, the liquid level in the aging tank gradually rises. The material in the aging tank is controlled to be maintained at 12.0Kg through the interlocking of the aging tank level gauge and the solenoid valve, and carbon dioxide is used as the pressure supplement to maintain the aging tank pressure of 1.8MPa. The aged material is transferred to a flash tank, and after carbon dioxide is discharged, it is distilled under reduced pressure. Under this equilibrium, the aging time of the material in the aging tank is about 30 minutes, and the conversion rate of alkylene oxide reaches 99.9%. After continuous operation for 12h, about 192Kg of ethylene carbonate (selectivity>99.5%) was obtained, and the remaining 96Kg of ethylene carbonate residue containing catalyst was recycled for use. This method can realize an annual output of 140 tons of ethylene carbonate in a 20L circulating spray device.

Example 9: Addition of 4.0Kg ethylene carbonate containing 2.7g "electrophilic-nucleophilic" bifunctional catalyst in a circulating jet reactor with an effective volume of 20L, wherein the "electrophilic" moiety is Zn3[Fe( _CN ) ₆ ] ₂ ·2.1[ZnCl ₂ ]·1.8 ^t BuOH1.2H ₂ O, the "nucleophilic" part is tetrabutylammonium iodide, and the mass ratio of the two is 1:2. The reaction device was started, and the starting material was heated to 180° C. through a heat exchanger, and carbon dioxide was introduced into the reaction system until the pressure was 5.0 MPa. The aging tank was heated to 180 ℃ through a heat exchanger, and carbon dioxide was introduced to the aging tank until the pressure was 4.8 MPa. Prepare a mixed solution of ethylene carbonate and the above-mentioned "electrophilic-nucleophilic" bifunctional catalyst with a mass ratio of 1000:1, add ethylene oxide at a speed of 8.0Kg/h, and add catalyst-containing ethylene carbonate at a speed of 8.0Kg/h Mixed liquid (to be maintained above 40°C), control the mass ratio of ethylene oxide to ethylene carbonate to 1:1, continue to supplement carbon dioxide (the speed is maintained at 7.8 ~ 8.0Kg/h), and the control system pressure is maintained at 5.0MPa. During the feeding process, the material in the reactor is controlled by the interlocking of the liquid level gauge and the solenoid valve to maintain 4Kg, and the material growing at the bottom of the jet reactor is pressed into the aging tank. Complete all reactions. As the material is added, the liquid level in the aging tank gradually rises. The material in the aging tank is controlled to be maintained at 12.0Kg through the interlocking of the aging tank level gauge and the solenoid valve, and carbon dioxide is used as pressure supplement to maintain the aging tank pressure of 4.8MPa. The aged material is transferred to a flash tank, and after carbon dioxide is discharged, it is distilled under reduced pressure. Under this equilibrium, the aging time of the material in the aging tank is about 30 minutes, and the conversion rate of alkylene oxide reaches 99.9%. After continuous operation for 12h, about 192Kg of ethylene carbonate (selectivity>99.5%) was obtained, and the remaining 96Kg of ethylene carbonate residue containing catalyst was recycled for use. This method can realize an annual output of 140 tons of ethylene carbonate in a 20L circulating spray device.

Example 10: Addition of 4.0Kg ethylene carbonate containing 9g "electrophilic-nucleophilic" bifunctional catalyst in a circulating jet reactor with an effective volume of 20L, where the "electrophilic" moiety is Zn ₃ [Fe(CN) ₆ ] ₂ ·2.1[ZnCl ₂ ]·1.8 ^t BuOH1.2H ₂ O, the "nucleophilic" part is tetrabutylammonium iodide, and the mass ratio of the two is 1:2. The reaction device was started, and the starting material was heated to 110° C. through a heat exchanger, and carbon dioxide was introduced into the reaction system until the pressure was 2.0 MPa. The aging tank was heated to 110° C. through a heat exchanger, and carbon dioxide was introduced until the pressure of the aging tank was 1.8 MPa. Prepare a mixed solution of ethylene carbonate and the above-mentioned "electrophilic-nucleophilic" bifunctional catalyst with a mass ratio of 400:1, add ethylene oxide at a speed of 1.2Kg/h, and add catalyst-containing ethylene carbonate at a speed of 24.0Kg/h Mixed solution (to be maintained above 40°C), the mass ratio of ethylene oxide and ethylene carbonate is controlled to be 1:1, carbon dioxide is continuously supplemented (the speed is maintained at 1.0-1.2Kg/h), and the pressure of the control system is maintained at 2.0MPa. During the feeding process, the material in the reactor is controlled by the interlocking of the liquid level gauge and the solenoid valve to maintain 4Kg, and the material growing at the bottom of the jet reactor is pressed into the aging tank. Complete all reactions. As the material is added, the liquid level in the aging tank gradually increases. The material in the aging tank is controlled to be maintained at 5.9Kg through the interlocking of the aging tank level gauge and the solenoid valve, and carbon dioxide is used as the pressure supplement to maintain the aging tank pressure of 1.8MPa. The aged material is transferred to a flash tank, and after carbon dioxide is discharged, it is distilled under reduced pressure. Under this equilibrium, the aging time of the material in the aging tank is about 20 minutes, and the conversion rate of alkylene oxide reaches 99.9%. After continuous operation for 12h, about 28.8Kg of ethylene carbonate (selectivity>99.5%) was obtained, and the remaining 288Kg of ethylene carbonate residue containing catalyst was recycled for use. This method can realize an annual output of 21 tons of ethylene carbonate in a 20L circulating spray device.

Example 11: Addition of 4.0Kg ethylene carbonate containing 10g "electrophilic-nucleophilic" bifunctional catalyst in a circulating jet reactor with an effective volume of 20L, wherein the "electrophilic" moiety is Zn3[Fe( _{CN)6 ] 2} ·2.1[ZnCl ₂ ]·1.8 ^t BuOH1.2H ₂ O, the "nucleophilic" part is tetrabutylammonium iodide, and the mass ratio of the two is 1:2. The reaction device was started, and the starting material was heated to 110° C. through a heat exchanger, and carbon dioxide was introduced into the reaction system until the pressure was 2.0 MPa. The aging tank was heated to 110° C. through a heat exchanger, and carbon dioxide was introduced until the pressure of the aging tank was 1.8 MPa. Prepare a mixed solution of ethylene carbonate and the above-mentioned "electrophilic-nucleophilic" bifunctional catalyst with a mass ratio of 10:1, add ethylene oxide at a rate of 8.0Kg/h, and add catalyst-containing ethylene carbonate at a rate of 0.4Kg/h Mixed solution (maintain above 40℃), control the mass ratio of ethylene oxide and ethylene carbonate to 1:1, continue to supplement carbon dioxide (the speed is maintained at 7.8-8.0Kg/h), and control the system pressure to maintain at 2.0MPa. During the feeding process, the material in the reactor is controlled by the interlocking of the liquid level gauge and the solenoid valve to maintain 4Kg, and the material growing at the bottom of the jet reactor is pressed into the aging tank. Complete all reactions. As the material is added, the liquid level in the aging tank gradually rises. The material in the aging tank is controlled to be maintained at 8.2Kg through the interlocking of the aging tank level gauge and the solenoid valve, and carbon dioxide is used as the pressure supplement to maintain the aging tank pressure of 1.8MPa. The aged material is transferred to a flash tank, and after carbon dioxide is discharged, it is distilled under reduced pressure. Under this equilibrium, the aging time of the material in the aging tank is about 30 minutes, and the conversion rate of alkylene oxide reaches 99.9%. After continuous operation for 12h, about 192Kg of ethylene carbonate (selectivity>99.5%) was obtained, and the remaining 5.3Kg of ethylene carbonate residue containing catalyst was recycled for use. This method can realize an annual output of 140 tons of ethylene carbonate in a 20L circulating spray device.

Example 12: Addition of 4.0Kg ethylene carbonate containing 0.16g "electrophilic-nucleophilic" bifunctional catalyst in a circulating jet reactor with an effective volume of 20L, wherein the "electrophilic" moiety is Zn ₃ [Fe(CN) ₆ ] ₂ ·2.1[ZnCl ₂ ]·1.8 ^t BuOH1.2 H ₂ O, the "nucleophilic" part is tetrabutylammonium iodide, and the mass ratio of the two is 1:2. The reaction device was started, and the starting material was heated to 180° C. through a heat exchanger, and carbon dioxide was introduced into the reaction system until the pressure was 5.0 MPa. The aging tank was heated to 180 ℃ through a heat exchanger, and carbon dioxide was introduced to the aging tank until the pressure was 4.8 MPa. Prepare a mixed solution of ethylene carbonate and the above-mentioned "electrophilic-nucleophilic" bifunctional catalyst with a mass ratio of 5000:1, add ethylene oxide at a speed of 4.0Kg/h, and add catalyst-containing ethylene carbonate at a speed of 2.0Kg/h Mixed solution (maintain above 40°C), control the mass ratio of ethylene oxide and ethylene carbonate to 1:1, continue to supplement carbon dioxide (the speed is maintained at 3.8-4.0Kg/h), and control the system pressure to maintain at 5.0MPa. During the feeding process, the material in the reactor is controlled by the interlocking of the liquid level gauge and the solenoid valve to maintain 4Kg, and the material growing at the bottom of the jet reactor is pressed into the aging tank. Complete all reactions. As the material is added, the liquid level in the aging tank gradually rises. The material in the aging tank is controlled to be maintained at 5Kg through the interlocking of the aging tank level gauge and the solenoid valve, and carbon dioxide is used as the pressure supplement to maintain the aging tank pressure of 4.8MPa. The aged material is transferred to a flash tank, and after carbon dioxide is discharged, it is distilled under reduced pressure. Under this equilibrium, the aging time of the material in the aging tank is about 30 minutes, and the conversion rate of alkylene oxide reaches 99.9%. After continuous operation for 12h, about 96Kg of ethylene carbonate (selectivity>99.5%) was obtained, and the remaining 24Kg of ethylene carbonate residue containing catalyst was recycled for use. This method can realize an annual output of 70 tons of ethylene carbonate in a 20L circulating spray device.

Claims (10)

1. a cyclic jet type continuous reaction process for preparing cyclic carbonate, is characterized in that, adopts the cyclic jet reactor, takes " electrophilic-nucleophilic " bifunctional system as catalyzer, at the reaction pressure of 0.4～5.0MPa and Under the reaction temperature of 25～180 ℃, carbon dioxide and alkylene oxide are used as raw materials to carry out coupling reaction to continuously prepare cyclic carbonate; the specific reaction process is as follows: A certain amount of cyclic carbonate containing catalyst is added to the circulating jet reactor, the circulating pump is turned on, the starting material is heated to the reaction temperature through the heat exchanger, and carbon dioxide is introduced to the reaction pressure; Oxyalkane and cyclic carbonate dissolved with catalyst, and carbon dioxide was added to keep the reaction pressure constant; after the material liquid level in the circulating jet reactor reached the set value, the reaction material began to transfer to the aging tank, and the material liquid in the aging tank was to be After rising to a certain height and ensuring that the conversion rate of alkylene oxide reaches 99.9%, the reaction material begins to be transferred to the flash tank, carbon dioxide is discharged, and vacuum distillation is performed to obtain cyclic carbonate, and the residual liquid containing the catalyst is recycled; the whole process In the process, it is necessary to control the balance of materials in and out of the circulating jet reactor, aging tank and flash tank, and maintain a stable state of continuous feeding reaction and discharging collection; In the continuously added material, the mass ratio of alkylene oxide to catalyst is 5:1 to 50000:1; In the continuously added material, the mass ratio of alkylene oxide to cyclic carbonate is 1:20-20:1. 2. a kind of circulating spray type continuous reaction process for preparing cyclic carbonate according to claim 1 is characterized in that, in the described "electrophilic-nucleophilic" bifunctional catalyst, the "electrophilic" part and "electrophilic" The mass ratio of the "nucleophilic" part is 1:1 to 1:50; The general formula of the "electrophilic" part is M ¹ _a [M ² (CN) _b L ¹ _c ] _d · x[M ³ _m X _n ] · yL ² · zH ₂ O; in the formula, M ¹ and M ³ are selected From Zn ²⁺ , Co ²⁺ , Ni ²⁺ , Fe ²⁺ , Fe ³⁺ , ^{Ca 2+} , Mg ²⁺ , Cu ²⁺ , Cr ³⁺ , Al ³⁺ , Sn ²⁺ , Cd ²⁺ or Pb ²⁺ ; M ² is selected from Co ³⁺ , Ni ²⁺ , Fe ²⁺ , Fe ³⁺ , Cr ^{3 +} , Mn ³⁺ or Cu ²⁺ ; L ¹ is an internal ligand that coordinates with M ² ; X is an aryloxy anion or an organic carboxylate anion; L ² is selected from a water-soluble heteroatom organic complexing agent; a, b, d, m and n are zero or satisfy the balance of positive and negative charges, wherein b is a positive integer ; x is positive, c, y and z are zero or positive; The general formula of the "nucleophilic" moiety is a salt of R ¹ R ² ₃ YX ¹ , wherein: R ¹ is C ₁ -C ₁₆ alkyl, R ² is C ₁ -C ₆ alkyl or phenyl; Y is nitrogen , phosphorus or arsenic; X ¹ is Cl ^-1 , Br ^-1 , I ^-1 , NO ₃ ^-1 , CH ₃ COO ^-1 , ClO ₄ ^-1 , BF ₄ ^-1 , OH ^-1 , BPh ₄ ^-1 Or N ₃ ^-1 monovalent anion. 3. a kind of circulating spray type continuous reaction process for preparing cyclic carbonate according to claim ¹ and 2, is characterized in that, L is selected from the monodentate that forms with C, H, N, O, P and S or polydentate ligand; L ² is selected from one or more mixtures of alcohol, aldehyde, ketone, ether, ester, amide, urea, nitrile, and sulfide; X is F ^- , Cl ^- , Br ^- , I ^- , NO ₃ ^- , CH ₃ COO ^- , SO ₄ ^2- , methylbenzoate, p-toluenesulfonate, o-nitrophenol oxygen, p-nitrophenol oxygen, m-nitrophenol oxygen, etc. Aryloxy anion or organic carboxylate anion. 4. a kind of cyclic injection type continuous reaction process for preparing cyclic carbonate according to claim 1 and 2, is characterized in that, the mass ratio of the alkylene oxide and the catalyst in the material that continues to add is 100:1～500 :1. 5. a kind of cyclic injection type continuous reaction process for preparing cyclic carbonate according to claim 3, is characterized in that, the mass ratio of the alkylene oxide and catalyst in the material continuously added is 100:1～500:1 . 6. a kind of cyclic injection type continuous reaction process of preparing cyclic carbonate according to claim 1,2 or 5 is characterized in that, the mass ratio of the alkylene oxide in the material that continues to add and cyclic carbonate is 1:2 to 2:1. 7. a kind of cyclic injection type continuous reaction process for preparing cyclic carbonate according to claim 3, is characterized in that, the mass ratio of the alkylene oxide and cyclic carbonate in the material that continues to add is 1:2～ 2:1. 8. a kind of cyclic injection type continuous reaction process for preparing cyclic carbonate according to claim 4, is characterized in that, the mass ratio of the alkylene oxide and cyclic carbonate in the material that continues to add is 1:2～ 2:1. 9. according to claim 1,2,5,7 or 8 described a kind of circulating spray type continuous reaction process of preparing cyclic carbonate, it is characterized in that, described alkylene oxide is ethylene oxide or epoxy propane. 10 . The cyclic jet continuous reaction process for preparing cyclic carbonate according to claim 6 , wherein the alkylene oxide is ethylene oxide or propylene oxide. 11 .

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