Heterogeneous catalytic reaction rectification synthesis method of cyclopropane compound

Abstract

The invention provides a heterogeneous catalytic reaction rectification synthesis method of a cyclopropane compound, belongs to the technical field of aerospace industrial fuel, and aims to solve the technical problems of low process integration level, difficulty in serialization, low production capacity and the like due to the fact that alkaline hydroxide is used as a catalyst in the prior art. A catalytic reaction rectifying tower is used as a reaction device, and a pyrazoline derivative is used as a reaction raw material to prepare the cyclopropane compound. The catalytic reaction rectifying tower comprises an upper rectifying section, a middle reaction section and a lower stripping section; the reaction section is filled with a catalyst, the pyrazoline derivative is fed from the upper part of the reaction section and is in contact with the catalyst to perform denitrification reaction, the cyclopropane compound is extracted from the top of the tower, and the unreacted pyrazoline derivative and ketazine compound are collected at the bottom of the tower. According to the invention, pyrazoline derivatives are continuously fed from the upper part of the reaction section and are in contact with a catalyst, products are continuously removed, reactants are left for continuous reaction, and the reaction is continuously carried out towards the direction of generating cyclopropane compounds; the coupling integration of reaction and rectification is realized, and the production capacity of products is improved on the whole.

Description

Technical Field

[0001] The invention belongs to the technical field of aviation industry fuel, and in particular relates to the synthesis of a cyclopropane compound. Background Art

[0002] my country has made remarkable progress in the green preparation technology of high energy density hydrocarbon fuels. By using advanced quantum chemical calculations, catalytic biology, new catalysts, and green engineering technologies, China has made important breakthroughs in the construction of strained ring structures through highly selective olefin addition / condensation reactions and the preparation of high energy aerospace fuels from biomass energy. It has achieved laboratory-level research and development of high energy density hydrocarbon fuels and high energy biofuels for Long March rockets, as well as industrial applications of a number of key fuels and aerospace models. At present, my country is at the world's leading level in the field of green production technology of high energy density hydrocarbon fuels.

[0003] Cyclopropane-based hydrocarbon fuels have attracted much attention in the industry due to their high density and high energy. Cyclopropane-based hydrocarbon fuels have multiple groups of three-membered carbon ring structural units, and their cyclopropane molecules have the largest ring tension (114KJ / mol) and the highest methylene unit combustion heat (697KJ / mol). Compared with conventional unsubstituted four-membered to eight-membered cycloalkanes, cyclopropane has the largest tension energy, which can significantly improve the molecular energy density. For example: tension energy: cyclopropane 114KJ / mol VS cyclobutane 110KJ / mol VS cyclopentane 27KJ / mol VS cyclohexane (almost no tension). At present, cyclopropane-based hydrocarbon high-energy fuels are mainly obtained by high-temperature denitrogenation of 2-pyrazoline, and the reaction equation is shown in Formula III below:

[0004]

[0005] At present, the preparation method suitable for industrial amplification of 2-pyrazoline high temperature denitrogenation is rarely reported. Only patent publication number CN114436731A discloses a preparation method (laboratory scale) of cyclopropane derivatives, and the preparation route mainly adopts intermittent kettle reaction, and the yield can reach 97% at most. Although this route can also achieve high yield, the production efficiency is low, and continuous operation cannot be achieved. At the same time, the catalyst NaOH or KOH cannot be recycled, and a large amount of alkali residue solid waste will be produced, which is unfriendly to the environment. Summary of the invention

[0006] In view of the technical problem of low production efficiency of cyclopropane derivatives, the present invention proposes a heterogeneous catalytic reaction distillation synthesis method for cyclopropane compounds, which adopts a high-purity solid base catalyst, and effectively realizes the continuous production of cyclopropane compounds by organically coupling the reaction unit with the distillation unit, and the production efficiency is significantly improved. The efficiency of laboratory-scale production of cyclopropane compounds reaches 404.6g / h. At the same time, the high-purity solid base catalyst is fixed in the reaction section of the reaction distillation device, and can be regularly supplemented and replaced, which avoids the loss of the alkaline catalyst with the cleaning kettle during the intermittent batch material change, and further avoids the generation of alkali slag solid waste during the intermittent batch material change.

[0007] In order to achieve the above object, the technical solution of the present invention is achieved as follows:

[0008] A heterogeneous catalytic reaction distillation synthesis method for cyclopropane compounds, which adopts a catalytic reaction distillation tower as a reaction device and a pyrazoline derivative as a reaction raw material to prepare the cyclopropane compound; the catalytic reaction distillation tower comprises an upper distillation section, a middle reaction section and a lower stripping section; the reaction section is filled with a catalyst, the pyrazoline derivative is fed from the top of the reaction section to contact with the catalyst, a denitrogenation reaction occurs, the cyclopropane compound is extracted at the top of the tower, and the unreacted pyrazoline derivative and ketoazine compound are collected at the bottom of the tower.

[0009] The structural formula of the pyrazoline derivative is shown in Formula I below: The structural formula of the cyclopropane compound is shown in Formula II below:

[0010]

[0011] The catalyst is a solid base catalyst, which comprises an active component and a carrier; the active component is KOH, NaOH, K2CO3 or Na2CO3; and the carrier is Al2O3, MgO or activated carbon.

[0012] Preferably, the solid base catalyst is any one of KOH / Al2O3, NaOH / Al2O3, KOH / Activated carbon, K2CO3 / MgO, KOH / MgO, Na2CO3 / Al2O3 and K2CO3 / MgO; more preferably, the solid base catalyst is any one of KOH / Al2O3 and NaOH / Al2O3.

[0013] The particle size of the solid base catalyst is 1-5 mm, and the active component loading rate is 13-30 wt %.

[0014] The filler in the catalytic reaction distillation tower is bulk filler, the volume ratio of catalyst to bulk filler is 1:1, and the filling height of the catalyst in the catalytic reaction distillation tower is 0.15-0.35m (ie, the height of the reaction section).

[0015] The filler is a θ-ring filler; preferably, the θ-ring filler is a stainless steel bulk θ-ring filler.

[0016] The liquid hourly space velocity of the pyrazoline derivative is 1.7-6.3h -1 .

[0017] The feed temperature of the pyrazoline derivative is 195-210°C, preferably 205°C.

[0018] The temperature of the heavy reaction section of the catalytic reaction distillation tower is 215-225°C, preferably 218°C.

[0019] The catalytic reaction distillation tower is provided with a reboiler, and the temperature of the reboiler is 230-240°C, preferably 235°C.

[0020] Beneficial effects of the present invention: 1. The present invention injects the pyrazoline derivative and the catalyst into the catalytic reaction distillation device respectively, controls the kettle temperature, the catalyst filling amount, the feeding and discharging speed, and the reflux ratio, and obtains the cyclopropane compound, thereby realizing efficient and continuous production of the cyclopropane compound.

[0021] 2. In the present invention, a high-purity solid base catalyst is used for the first time. By organically coupling the reaction unit with the distillation unit, the continuous production of cyclopropane compounds is effectively achieved, the production efficiency is significantly improved, and the efficiency of laboratory-scale production of cyclopropane compounds reaches 404.6 g / h.

[0022] 3. In the present invention, the high-purity solid alkali catalyst is fixed in the reaction section of the reaction distillation device and can be replenished and replaced regularly, thereby avoiding the loss of the alkali catalyst with the cleaning kettle during intermittent batch material change and further avoiding the generation of alkali slag solid waste during intermittent batch material change. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0024] Figure 1 This is the reaction formula for synthesizing cyclopropane compounds from pyrazoline derivatives.

[0025] Figure 2 A process flow chart of the device system used to synthesize cyclopropane compounds from pyrazoline derivatives in an embodiment of the present invention.

[0026] In the figure: I, catalytic reaction distillation tower; II, negative pressure distillation tower; 1, first preheater; 2, upper feed pipe of reaction section; 3, first condenser; 4, first reflux controller; 5, first reflux pipe; 6, first reboiler; 7, bottom product discharge pipe; 8, top crude product tank; 9, bottom product tank; 10, second preheater; 11, second condenser; 12, second reflux controller; 13, second reflux pipe; 14, top light component tank; 15, second reboiler; 16, cyclopropane product discharge pipe; 17, refined cyclopropane product tank.

[0027] Figure 3 This is the gas chromatogram of the cyclopropane compound in Example 1.

[0028] Figure 4 This is the gas phase mass spectrum of the cyclopropane compound in Example 1.

[0029] Figure 5 This is the gas chromatographic spectrum of the cyclopropane compound of Example 2.

[0030] Figure 6 This is the gas chromatogram of the cyclopropane compound of Example 3.

[0031] Figure 7 This is the gas chromatogram of the cyclopropane compound of Example 4. DETAILED DESCRIPTION

[0032] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0033] The heterogeneous catalytic reaction distillation synthesis of the cyclopropane compound of the present invention is carried out using the following reaction system: Figure 2As shown, it includes a catalytic reaction distillation tower I and a negative pressure distillation tower II, the catalytic reaction distillation tower I includes an upper distillation section, a middle reaction section and a lower stripping section, and the reaction section is filled with a catalyst; the negative pressure distillation tower II is a conventional distillation tower. The pyrazoline derivative is heated by the first preheater 1 and input into the catalytic reaction distillation tower I through the upper feed pipe 2 of the reaction section. The first condenser 3 is connected above the catalytic reaction distillation tower I, the first condenser 3 is connected to the first reflux controller 4, and is connected to the catalytic reaction distillation tower I through the first reflux pipe 5, and the condensed cyclopropane compound is stored in the top crude product tank 8. The bottom of the catalytic reaction distillation tower I is provided with a first reboiler 6, which is heated by the first reboiler 6 and returns to the inside of the catalytic reaction distillation tower I, and the bottom liquid is pumped to the bottom product tank 9 through the bottom product discharge pipe 7 for storage. The top crude product tank 8 is connected to the negative pressure distillation tower II, and a second preheater 10 is provided between the two, and the crude product of the cyclopropane compound is further distilled by the negative pressure distillation tower II. The top of the negative pressure distillation tower II is connected to a second condenser 11, which is connected to a second reflux controller 12 and connected to the catalytic reaction distillation tower I through a second reflux pipe 13. The light components after the condenser are stored in a light component tank 14 at the top of the tower; a second reboiler 15 is provided at the bottom, and the components are heated by the second reboiler 15 and returned to the inside of the negative pressure distillation tower II. The bottom liquid is pumped to the refined cyclopropane product tank through a cyclopropane product discharge pipe 16 for storage. The following embodiments all use this device

[0034] In the following examples of the present invention, 3,5-methyl-5-methylpyrazoline is used to prepare 1,2-methyl-2-methylcyclopropane, and the reaction formula is as follows: Figure 1 As shown, R1 is methyl. It should be noted that the reaction material is a 3,5-methyl-5-methylpyrazoline mixture (the main components are 50wt% of 3,5-methyl-5-methylpyrazoline, 48wt% of the synthetic raw material of acetone azine, 2wt% of ketone and other components). The main reason for using the mixture as feed is that the synthetic raw materials acetone azine and 3,5-methyl-5-methylpyrazoline are isomers with similar boiling points. Traditional distillation separation is difficult and costly, so they are not separated and purified in the process technology route.

[0035] Example 1

[0036] This embodiment specifically includes the following steps:

[0037] After the 3,5-methyl-5-methylpyrazoline mixture passes through the first preheater 1, it is transported to the catalytic reaction distillation tower I through the upper feed pipe 2 of the reaction section, and is fed from the upper part of the reaction section. The feed temperature is 205°C, the KOH / Al2O3 catalyst (1-2 mm small balls, loading rate 15%, and the volume ratio of the θ ring filler is 1:1) is filled with a height of 0.15m, and the mass space velocity is 2.8h -1, the temperature of the reaction section is maintained at 218°C. The tower is operated at normal pressure, with a top temperature of 153°C. 1,2-methyl-2-methylcyclopropane and other light components (1,2-methyl-2-methylcyclopropane content 98%) are extracted from the top of the tower through the first condenser 3 and enter the top crude product tank 8. The temperature of the first reboiler 6 at the bottom of the tower is 230°C, and the bottom liquid composed of acetone azine and unreacted 3,5-methyl-5-methylpyrazoline (3,5-methyl-5-methylpyrazoline content <1.9%) is extracted through the bottom product discharge pipe to the bottom product tank 9.

[0038] The top crude product is then continuously fed from the top crude product tank 8 through the second preheater 10 (preheated to 30° C.) into the negative pressure distillation tower IIⅡ (middle feed) at a feed rate of 80 mL / min. The tower is operated under negative pressure, and the system vacuum is maintained at -0.093±0.001MPa. The tower top temperature is 43±1°C. A second condenser 11 is provided on the tower top with a reflux ratio of 1:5. Light components (mainly ketones, etc., with a purity of >99.0%, and a 1,2-methyl-2-methylcyclopropane content of <0.02%) are produced to a light component tank 14 on the tower top. A second reboiler 15 is provided at the tower bottom with a tower bottom temperature of 120°C. Refined product 1,2-methyl-2-methylcyclopropane (with a purity of >99.4%, a ketone content of <0.015%, and a content of other substances of <0.5%) is continuously produced through a cyclopropane product discharge pipe 16 to a refined cyclopropane product tank. The production flow rate is 50mL / min.

[0039] In this example, the total mass of the target product obtained is 110.0 g / h, the purity is greater than 99.4%, the yield is 98.0%, and the gas phase spectrum is as follows: Figure 3 and 4 shown.

[0040] Example 2

[0041] This embodiment specifically includes the following steps:

[0042] After the 3,5-methyl-5-methylpyrazoline mixture passes through the first preheater 1, it is transported to the catalytic reaction distillation tower I through the upper feed pipe 2 of the reaction section, and is fed from the upper part of the reaction section. The feed temperature is 205°C, the KOH / Al2O3 catalyst (1-2 mm small balls, loading rate 15%, and the volume ratio of the θ ring filler is 1:1) is filled with a height of 0.25m, and the mass space velocity is 1.7h -1, the temperature of the reaction section is maintained at 218°C. The tower is operated at normal pressure, with a top temperature of 153°C. 1,2-methyl-2-methylcyclopropane and other light components (1,2-methyl-2-methylcyclopropane content 98%) are extracted from the top of the tower through the first condenser 3 and enter the top crude product tank 8. The temperature of the first reboiler 6 at the bottom of the tower is 230°C, and the bottom liquid composed of acetone azine and unreacted 3,5-methyl-5-methylpyrazoline (3,5-methyl-5-methylpyrazoline content <0.95%) is extracted through the bottom product discharge pipe to the bottom product tank 9.

[0043] The top crude product is then continuously fed from the top crude product tank 8 through the second preheater 10 (preheated to 30° C.) into the negative pressure distillation tower IIⅡ (middle feed) at a feed rate of 80 mL / min. The tower is operated under negative pressure, and the system vacuum is maintained at -0.093±0.001MPa. The tower top temperature is 43±1°C. A second condenser 11 is provided on the tower top with a reflux ratio of 1:5. Light components (mainly ketones, etc., with a purity of >99.0%, and a 1,2-methyl-2-methylcyclopropane content of <0.02%) are produced to a light component tank 14 on the tower top. A second reboiler 15 is provided at the tower bottom with a tower bottom temperature of 120°C. Refined product 1,2-methyl-2-methylcyclopropane (with a purity of >99.4%, a ketone content of <0.015%, and a content of other substances of <0.5%) is continuously produced through a cyclopropane product discharge pipe 16 to a refined cyclopropane product tank. The production flow rate is 50mL / min.

[0044] In this example, the total mass of the target product obtained is 111.1 g / h, the purity is greater than 99.4%, the yield is 99.0%, and the gas phase spectrum is as follows: Figure 5 shown.

[0045] Example 3

[0046] This embodiment specifically includes the following steps:

[0047] After the 3,5-methyl-5-methylpyrazoline mixture passes through the first preheater 1, it is transported to the catalytic reaction distillation tower I through the upper feed pipe 2 of the reaction section, and is fed from the upper part of the reaction section. The feed temperature is 210°C, the KOH / Al2O3 catalyst (1-2 mm small balls, loading rate 15%, and the volume ratio with the θ ring filler is 1:1) is filled with a height of 0.25m, and the mass space velocity is 6.3h -1, the temperature of the reaction section is maintained at 225°C. The tower is operated at normal pressure, with a top temperature of 157°C. 1,2-methyl-2-methylcyclopropane and other light components (1,2-methyl-2-methylcyclopropane content 98%) are extracted from the top of the tower through the first condenser 3 and enter the top crude product tank 8. The temperature of the first reboiler 6 at the bottom of the tower is 240°C, and the bottom liquid composed of acetone azine and unreacted 3,5-methyl-5-methylpyrazoline (3,5-methyl-5-methylpyrazoline content <3.2%) is extracted through the bottom product discharge pipe to the bottom product tank 9.

[0048] The top crude product is then continuously fed from the top crude product tank 8 through the second preheater 10 (preheated to 30° C.) into the negative pressure distillation tower IIⅡ (middle feed) at a feed rate of 80 mL / min. The tower is operated under negative pressure, and the system vacuum is maintained at -0.093±0.001MPa. The tower top temperature is 43±1°C. A second condenser 11 is provided on the tower top with a reflux ratio of 1:5. Light components (mainly ketones, etc., with a purity of >99.0%, and a 1,2-methyl-2-methylcyclopropane content of <0.02%) are produced to a light component tank 14 on the tower top. A second reboiler 15 is provided at the tower bottom with a tower bottom temperature of 120°C. Refined product 1,2-methyl-2-methylcyclopropane (with a purity of >99.4%, a ketone content of <0.015%, and a content of other substances of <0.5%) is continuously produced through a cyclopropane product discharge pipe 16 to a refined cyclopropane product tank. The production flow rate is 50mL / min.

[0049] In this example, the total mass of the target product obtained is 404.6 g / h, the purity is greater than 99.4%, the yield is 96.5%, and the gas phase spectrum is as follows: Figure 6 shown.

[0050] Example 4

[0051] This embodiment specifically includes the following steps:

[0052] After the 3,5-methyl-5-methylpyrazoline mixture passes through the first preheater 1, it is transported to the catalytic reaction distillation tower I through the upper feed pipe 2 of the reaction section, and is fed from the upper part of the reaction section. The feed temperature is 195°C, the KOH / Al2O3 catalyst (1-2 mm small balls, loading rate 15%, and the volume ratio with the θ ring filler is 1:1) is filled with a height of 0.35m, and the mass space velocity is 3.7h -1, the temperature of the reaction section is maintained at 225°C. The tower is operated at normal pressure, with a top temperature of 157°C. 1,2-methyl-2-methylcyclopropane and other light components (1,2-methyl-2-methylcyclopropane content 98%) are extracted from the top of the tower through the first condenser 3 and enter the top crude product tank 8. The temperature of the first reboiler 6 at the bottom of the tower is 235°C, and the bottom liquid composed of acetone azine and unreacted 3,5-methyl-5-methylpyrazoline (3,5-methyl-5-methylpyrazoline content <1.4%) is extracted through the bottom product discharge pipe to the bottom product tank 9.

[0053] The top crude product is then continuously fed from the top crude product tank 8 through the second preheater 10 (preheated to 30° C.) into the negative pressure distillation tower IIⅡ (middle feed) at a feed rate of 80 mL / min. The tower is operated under negative pressure, and the system vacuum is maintained at -0.093±0.001MPa. The tower top temperature is 43±1°C. A second condenser 11 is provided on the tower top with a reflux ratio of 1:5. Light components (mainly ketones, etc., with a purity of >99.0%, and a 1,2-methyl-2-methylcyclopropane content of <0.02%) are produced to a light component tank 14 on the tower top. A second reboiler 15 is provided at the tower bottom with a tower bottom temperature of 120°C. Refined product 1,2-methyl-2-methylcyclopropane (with a purity of >99.4%, a ketone content of <0.015%, and a content of other substances of <0.5%) is continuously produced through a cyclopropane product discharge pipe 16 to a refined cyclopropane product tank. The production flow rate is 50mL / min.

[0054] In this example, the total mass of the target product obtained is 258.1 g / h, the purity is greater than 99.4%, the yield is 98.5%, and the gas phase spectrum is as follows: Figure 7 shown.

[0055] Comparative Example 1

[0056] (1) Weigh 282.0 g of a 3,5-methyl-5-methylpyrazoline mixture, add it to a 500 mL flask, stir it at a stirring speed of 200 rpm at room temperature, and add 10 wt % potassium hydroxide (28.2 g) thereto; after fully stirring for 2 h, stop stirring, let the liquid stand for 50 min, separate the lower aqueous phase by liquid separation, and collect 280.0 g of the upper liquid to obtain a dry pyrazoline compound;

[0057] (2) at room temperature, the dried pyrazoline mixture obtained in step 1) was transferred to a reaction kettle, stirred at a stirring speed of 300 rpm, and 20 wt % potassium hydroxide (56 g) was added to the reaction kettle; after the addition was completed, a reaction solution was obtained;

[0058] (3) The reaction liquid was heated to 160° C. while being stirred continuously, and a total of 5.6 g of low-boiling point compounds were removed by distillation. After no more distilled liquid was produced, the reaction liquid was heated until the temperature of the reaction liquid reached 190° C., and the condensate produced was collected.

[0059] (4) Continue heating the reaction solution to 210°C at a heating rate of 5°C / h, keep the temperature at the current temperature, and continue collecting the condensate until no more condensate is produced. The obtained condensate is recorded as liquid A, totaling 45.0 g;

[0060] (5) The reaction solution was kept warm for 3 h, and the condensate produced was collected. The reaction solution was then heated to 230 °C at a heating rate of 3 °C / h, and kept warm at the current temperature. The condensate was continuously collected until no condensate was produced. The collected condensate was recorded as liquid B, totaling 64.4 g.

[0061] (6) Liquid A and liquid B are fully mixed to obtain the target product.

[0062] In this comparative example, the total mass of the target product obtained was 109.4 g, the yield was 97.5%, and the total time was 14 h.

[0063] Examples 1-4 fully demonstrate that the process involved in this patent is feasible. Compared with Comparative Example 1, the preparation efficiency is greatly improved, and the continuous preparation of cyclopropane compounds is effectively realized.

[0064] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A heterogeneous catalytic reaction distillation synthesis method for cyclopropane compounds, characterized in that: A catalytic reaction distillation tower is used as a reaction device, and a pyrazoline derivative is used as a reaction raw material to prepare a cyclopropane compound; the catalytic reaction distillation tower comprises an upper distillation section, a middle reaction section and a lower stripping section; the reaction section is filled with a catalyst, the pyrazoline derivative is fed from the top of the reaction section to contact with the catalyst, a denitrogenation reaction occurs, the cyclopropane compound is extracted at the top of the tower, and the unreacted pyrazoline derivative and ketoazine compound are collected at the bottom of the tower.

2. The heterogeneous catalytic reaction distillation synthesis method of cyclopropane compounds according to claim 1, characterized in that: The structural formula of the pyrazoline derivative is shown in Formula I below: The structural formula of the cyclopropane compound is shown in Formula II below:

3. The heterogeneous catalytic reaction distillation synthesis method of cyclopropane compounds according to claim 2, characterized in that ,, the catalyst is a solid base catalyst, which includes an active component and a carrier; the active component is KOH, NaOH, K2CO3 or Na2CO3; the carrier is Al2O3, MgO or activated carbon.

4. The heterogeneous catalytic reaction distillation synthesis method of cyclopropane compounds according to claim 3, characterized in that: The particle size of the solid base catalyst is 1-5 mm, and the active component loading rate is 13-30 wt %.

5. The heterogeneous catalytic reaction distillation synthesis method of cyclopropane compounds according to claim 4, characterized in that: The filler in the catalytic reaction distillation tower is bulk filler, the volume ratio of catalyst to bulk filler is 1:1, and the filling height of the catalyst in the catalytic reaction distillation tower is 0.15-0.35m.

6. The heterogeneous catalytic reaction distillation synthesis method of cyclopropane compounds according to claim 5, characterized in that: The packing is a θ ring packing.

7. The heterogeneous catalytic reaction distillation synthesis method of cyclopropane compounds according to any one of claims 1 to 6, characterized in that: The liquid hourly space velocity of the pyrazoline derivative is 1.7-6.3h -1 .

8. The heterogeneous catalytic reaction distillation synthesis method of cyclopropane compounds according to claim 7, characterized in that: The feeding temperature of the pyrazoline derivative is 195-210°C.

9. The heterogeneous catalytic reaction distillation synthesis method of cyclopropane compounds according to claim 8, characterized in that: The temperature of the heavy reaction section of the catalytic reaction distillation tower is 215-225°C.

10. The heterogeneous catalytic reaction distillation synthesis method of cyclopropane compounds according to claim 1, characterized in that: The catalytic reaction distillation tower is provided with a reboiler, and the temperature of the reboiler is 230-240°C.

Images