Process for the carbonylation of cyclic olefins

Abstract

This invention relates to the field of organic synthesis, specifically to a method for the carbonylation of cycloolefins. The method is carried out in an apparatus comprising a shell-and-tube reactor. The reactor includes a shell and a tube located within and penetrating the shell, the tube wall having perforations for the passage of a limited gaseous feedstock. The tube has a gaseous feedstock inlet and an unreacted gaseous feedstock outlet at both ends penetrating the shell, while the shell has a liquid feedstock inlet and a product outlet. The method includes: feeding a solution containing a catalyst and cycloolefins into the shell side of the reactor; feeding a gaseous phase containing CO into the tube side of the reactor; and allowing some CO to permeate through the perforations in the tube wall into the tube side to react with the solution containing the catalyst and cycloolefins. This invention significantly enhances mass and heat transfer in the gas-liquid two-phase reaction, significantly improves the conversion rate of cycloolefins and the selectivity of the carbonylation product, increases reaction efficiency, and shortens reaction time.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis, and more specifically to a method for carbonylation of cycloolefins. Background Technology

[0002] Olefin carbonylation can convert olefins into esters in one step, followed by the preparation of amines via ammoniation and acids via hydrolysis. This process boasts high atom utilization and is environmentally friendly, making it a promising method for the high-value utilization of olefins. More importantly, the carbonylation of cyclic dienes can prepare diesters with aliphatic rings, which have potential applications as polymerizable monomers in the preparation of high-performance polyamides.

[0003] The carbonylation reaction of cycloolefins is a gas-liquid two-phase reaction due to the presence of carbon monoxide as a reactant. In traditional batch reactors, the gas-liquid interface is small, resulting in insufficient contact of reactants and low reaction efficiency.

[0004] Olefin carbonylation catalysts are mainly complexes formed by coordination of a central metal ion and related phosphine ligands. They are characterized by being soluble in the reaction system to form a homogeneous reaction liquid, and the presence of moisture and oxygen in the air can deactivate the catalyst, making it difficult to separate and reuse it using conventional methods. Summary of the Invention

[0005] The purpose of this invention is to overcome the aforementioned problems in the prior art and provide a method for the carbonylation of cycloolefins, which can improve the conversion rate of cycloolefins and the selectivity of products, and improve reaction efficiency.

[0006] To achieve the above objectives, the present invention provides a method for the carbonylation of cyclic olefins, the method being carried out in an apparatus comprising a shell-and-tube reactor, the shell-and-tube reactor comprising:

[0007] The shell, and a tube located inside and penetrating the shell, the tube wall having holes for the passage of a limited gaseous material;

[0008] The tube passing through both ends of the shell has a gaseous raw material inlet and an unreacted gaseous raw material outlet, and the shell has a liquid raw material inlet and a product outlet;

[0009] The method includes: feeding a solution containing a catalyst and cyclic olefins into the shell side of a reactor, feeding a gas phase containing CO into the tube side of the reactor, and allowing some CO to enter the tube side through pores in the tube wall and react with the solution containing the catalyst and cyclic olefins.

[0010] Through the above technical solution, the present invention has the following advantages:

[0011] The method of this invention can significantly enhance mass and heat transfer in gas-liquid two-phase reactions, significantly improve the conversion rate of cycloolefins and the selectivity of carbonylation products, improve reaction efficiency, and shorten reaction time.

[0012] In a preferred embodiment of the present invention, by applying membrane separation to the separation of cyclic olefin carbonylation products, the catalyst can be separated and reused, greatly reducing the synthesis cost and enabling the method to be carried out continuously. Attached Figure Description

[0013] Figure 1 This is a schematic diagram of the structure of a shell-and-tube microbubble reactor according to a preferred embodiment of the present invention.

[0014] Figure 2 This is a cross-sectional view of a shell-and-tube microbubble gas-liquid reactor according to a preferred embodiment of the present invention.

[0015] Figure 3 This is a schematic diagram of a system and process for a gas-liquid two-phase contact reaction according to a preferred embodiment of the present invention.

[0016] Figure 4 This is a schematic diagram of a membrane separator according to a preferred embodiment of the present invention.

[0017] Figure 4 In the middle section, 1 is the liquid inlet; 2 is the liquid outlet; 3 is the gas inlet; 4 is the gas and product outlet; 5 is the membrane tube body; and 6 is the membrane separator shell. Detailed Implementation

[0018] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0019] In this invention, along the direction of liquid flow, unless otherwise stated, directional terms are used such as upper part, which refers to the position of the reactor shell from top to bottom 0-30%; lower part, which refers to the position of the reactor shell from top to bottom 70-100%; top, which refers to the position of the shell from top to bottom 0-10%; and bottom, which refers to the position of the reactor shell from top to bottom 90-100%.

[0020] This invention provides a method for the carbonylation of cyclic olefins, which is carried out in an apparatus comprising a shell-and-tube reactor, such as... Figure 1 As shown, the shell-and-tube reactor includes: a shell, and a tube located inside the shell and penetrating the shell, the tube wall having holes for the passage of limited gaseous raw materials; the two ends of the tube penetrating the shell have gaseous raw material inlets and unreacted gaseous raw material outlets, and the shell has liquid raw material inlets and product outlets;

[0021] The method includes: feeding a solution containing a catalyst and cyclic olefins into the shell side of a reactor, feeding a gas phase containing CO into the tube side of the reactor, and allowing some CO to enter the tube side through pores in the tube wall and react with the solution containing the catalyst and cyclic olefins.

[0022] The method of this invention can significantly enhance mass and heat transfer in gas-liquid two-phase reactions, significantly improve the conversion rate of cycloolefins and the selectivity of carbonylation products, improve reaction efficiency, and shorten reaction time.

[0023] According to a preferred embodiment of the present invention, the pore size distribution of the pores on the tube wall ranges from 2 to 10 μm, preferably 3 to 5 μm. By adopting the aforementioned preferred embodiment, the conversion rate of cycloolefins and the selectivity of carbonylation products can be further improved, thereby further enhancing reaction efficiency and shortening reaction time.

[0024] According to a preferred embodiment of the present invention, the pore spacing on the tube wall is 5-30 μm, preferably 10-20 μm. By adopting the aforementioned preferred embodiment, the conversion rate of cycloolefins and the selectivity of carbonylation products can be further improved, thereby further enhancing reaction efficiency and shortening reaction time.

[0025] In this invention, the thickness of the tube wall is not particularly limited. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the wall thickness is 20-200 μm, preferably 50-100 μm.

[0026] According to a preferred embodiment of the present invention, the porosity of the tube wall is 20-50%, preferably 30-40%. By adopting the aforementioned preferred embodiment, the conversion rate of cycloolefins and the selectivity of carbonylation products can be further improved, thereby further enhancing reaction efficiency and shortening reaction time.

[0027] According to a preferred embodiment of the present invention, the equivalent diameter of the tube is 1-8 mm, preferably 2-4 mm. By adopting the aforementioned preferred embodiment, the gas-liquid contact effect can be further improved, and the degree of gas-liquid reaction can be enhanced.

[0028] According to a preferred embodiment of the present invention, when the number of tubes is greater than one, the tube spacing is 5-10 mm, preferably 6-8 mm. By adopting the aforementioned preferred solution, the gas-liquid contact effect can be further improved, and the degree of gas-liquid reaction can be enhanced.

[0029] According to a preferred embodiment of the present invention, the ratio of the total cross-sectional area of ​​the tube to the cross-sectional area of ​​the shell is 0.01-0.3, preferably 0.05-0.2. By adopting the aforementioned preferred embodiment, the conversion rate of cycloolefins and the selectivity of carbonylation products can be further improved, thereby further enhancing reaction efficiency and shortening reaction time.

[0030] In this invention, there are no special requirements for the shape of the reactor shell, as long as the solution of this invention can be implemented. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the shell is cylindrical with a length-to-diameter ratio of 2-10, preferably 3-5.

[0031] According to a preferred embodiment of the present invention, the equivalent diameter of the shell is 30-120 mm, preferably 50-80 mm.

[0032] According to a preferred embodiment of the present invention, the length of the housing is 60-500mm, preferably 200-300mm.

[0033] According to a preferred embodiment of the present invention, the shortest distance between the tube and the shell is 3-20 mm, preferably 5-10 mm.

[0034] According to a preferred embodiment of the present invention, a baffle is disposed within the space formed by the shell and the pipe wall, preferably with a distance of 10-50 mm between adjacent baffles, more preferably 20-40 mm. By adopting the aforementioned preferred embodiment, the gas-liquid contact effect can be further improved, and the degree of gas-liquid reaction can be enhanced.

[0035] According to a preferred embodiment of the present invention, the lower part of the shell is provided with a liquid raw material inlet, and the upper part of the shell is provided with a product outlet.

[0036] In this invention, the size of the liquid raw material inlet and the product outlet is not particularly limited and can be adjusted according to the specific situation. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the equivalent diameter of the liquid raw material inlet and the product outlet is 2-10 mm.

[0037] According to a preferred embodiment of the present invention, the gas source and / or gaseous raw material inlet and the unreacted gaseous raw material outlet are connected by a pipeline to ensure the recycling of gaseous raw materials and to maintain pressure.

[0038] In this invention, valve switches, heating devices, and driving devices are installed on any pipeline.

[0039] In this invention, the range of cyclic olefins is relatively wide. According to a preferred embodiment of this invention, the cyclic olefin is a cyclic olefin with 5-20 carbon atoms, preferably 5-12 carbon atoms, and preferably at least one of cyclopentadiene, dicyclopentadiene, norbornene, and norbornadiene.

[0040] In this invention, the conditions for the contact reaction can be selected from a wide range, as illustrated below, but this does not limit the scope of the invention.

[0041] According to a preferred embodiment of the present invention, the conditions for the contact reaction include: CO gas pressure of 1.0-10.0 MPa, preferably 2-5 MPa.

[0042] According to a preferred embodiment of the present invention, the conditions for the contact reaction include: a reaction temperature of 50-160°C, preferably 70-110°C.

[0043] In this invention, the catalyst can be a conventional catalyst in the art. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the catalyst is a metal ion-phosphonic acid catalyst, and the metal ion is a Group VIII and / or IIB metal.

[0044] According to a preferred embodiment of the present invention, the metal ion is at least one selected from Pd, Rh, Ni, Co, and Cu, preferably Pd.

[0045] According to a preferred embodiment of the present invention, the molar ratio of acid, phosphine, and palladium in the catalyst is 0.1-5∶1∶1-10, preferably 0.5-2∶1∶1-6.

[0046] According to a preferred embodiment of the present invention, the acid is at least one selected from methylbenzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, sulfuric acid, trifluoroacetic acid, sodium phosphate, and hydrochloric acid.

[0047] According to a preferred embodiment of the present invention, the phosphine is at least one selected from triphenylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, 1,2-bis(diphenylphosphine)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphine)butane, bis(diphenylphosphine)ferrocene, 1,3-bis(di-tert-butylphosphine)propane, and 1,2-bis(di-tert-butylphosphine)ethane.

[0048] According to a preferred embodiment of the present invention, in the solution containing the catalyst and cyclic olefins, the volume ratio of the catalyst to the solvent is 1:20-80, and the catalyst is a solution containing a palladium-phosphonic acid catalyst with a concentration of 5-30 mmol / L, calculated as palladium.

[0049] According to a preferred embodiment of the present invention, the volume ratio of the cyclic olefin to the solvent is 1:0.5-8, preferably 1:0.5-4.

[0050] According to a preferred embodiment of the present invention, the solvent is a C1-C8 alcohol solvent, preferably methanol.

[0051] According to a preferred embodiment of the present invention, the method further includes: passing the catalyst-containing product stream after the contact reaction into a membrane separator for membrane separation to obtain a permeate product and a catalyst-containing non-permeate stream, wherein the catalyst-containing non-permeate stream is recycled back into a solution containing the catalyst and cyclic olefins.

[0052] According to a preferred embodiment of the present invention, the membrane used for membrane separation is selected from at least one of carbon nanotubes, silica membranes, NaA zeolite membranes and ZSM-5 zeolite membranes, preferably silica membranes.

[0053] According to a preferred embodiment of the present invention, the pore size distribution of the membrane used for membrane separation is in the range of 0.5-2 nm, preferably 0.8-1 nm.

[0054] According to a preferred embodiment of the present invention, the membrane used for membrane separation has a thickness of 2-20 μm, preferably 5-10 μm.

[0055] According to a preferred embodiment of the present invention, the porosity of the membrane used for membrane separation is 10-40%, preferably 15-25%.

[0056] In the present invention as Figure 3 The system shown and Figure 4 In the membrane separator, the gas-liquid reaction process includes:

[0057] The catalyst, liquid reactants, and solvent are fed into a mixer for mixing. The mixed liquid feedstock is then fed into a shell-and-tube microbubble gas-liquid mixer in the microbubble reaction unit for reaction. After the reaction is complete, the reaction products are separated by membrane separation. A gaseous feedstock is injected to provide a carrier gas for blowing out the precipitated products on the permeate side of the membrane separator. The catalyst-free permeate is sent to a product collection tank, and the gas removed from it is sent to a waste gas treatment tank. The non-permeate containing the catalyst is recycled back to the reactor. The unreacted gaseous feedstock is recycled back to the gas source and / or the reactor for pressure maintenance. In this process, the membrane used in the separation unit of this invention cannot directly permeate all the solvent and product. The liquid permeates through the pressure difference across the membrane, and the liquid rejection rate is typically 20-70%, with better performance at 30-50%.

[0058] The present invention will be described in detail below through examples. In the following examples, the cyclic olefin raw materials are industrial products, and other raw materials are commercially available products from Sigma-Aldrich unless otherwise specified.

[0059] Example 1

[0060] In such Figure 3 The system shown is used in the experiment, and the structure and parameters of the reactor in the system are as follows: Figures 1-2 As shown, the membrane separator structure is as follows: Figure 4As shown, specifically, the pore size distribution on the tube wall is 3-5 μm; the spacing between the pores on the tube wall is 10 μm; the tube wall thickness is 100 μm; the porosity of the tube wall is 40%; the tube is a circular tube with a diameter of 3 mm; the number of tubes is 37 or 61, this embodiment uses 37 tubes with a tube spacing of 7.5 mm; the ratio of the total cross-sectional area of ​​the tubes to the cross-sectional area of ​​the shell is 0.093; the shell is cylindrical, with a length of 270 mm and a diameter of 60 mm; the shortest distance between the tubes and the shell is 6 mm; baffles are arranged in the space formed by the shell and the tube wall, with a distance of 30 mm between adjacent baffles; the membrane separation uses a silicon oxide membrane with a pore size distribution range of 0.8-1 nm; the membrane thickness is 10 μm; and the porosity is 20%.

[0061] Add 0.5 mmol of Pd(OAc)₂, 0.5 mmol of PPh₃, 0.25 mmol of trifluoroacetic acid, and 100 mL of anhydrous methanol to the catalyst tank and mix thoroughly with a stirrer. Add 400 mL of cyclopentadiene to the cyclic olefin tank and 200 mL of methanol to the methanol tank. Purify the reaction apparatus three times with carbon monoxide. Using a pump, pump the catalyst, cyclopentadiene, and methanol into the mixer at flow rates of 5 mL / h, 200 mL / h, and 100 mL / h, respectively. After thorough mixing, introduce the mixture into the microbubble reactor. Then, introduce carbon monoxide into the tube bundle of the microbubble reactor and gradually increase the pressure to 2.0 MPa. The temperature is slowly increased to 110℃, and the reaction product stream is fed into the membrane separation unit for separation. Simultaneously, carbon monoxide is introduced as a carrier gas to blow out the precipitated product from the permeate side of the membrane separator. The membrane rejection rate is 40%. The catalyst-free permeate is sent to a product collection tank, while the gas removed is sent to a waste gas treatment tank. The catalyst-containing non-permeate is recycled back to the reactor. Unreacted gaseous feedstock is recycled back to the gas source, i.e., the gas phase storage tank, for pressurization. After the reaction is complete, a sample is taken from the product collection tank and quantitatively analyzed using gas chromatography. The product contains no catalyst, the cyclopentadiene conversion rate is 99%, and the selectivity of the product dimethyl cyclopentanoate is 98%.

[0062] Example 2

[0063] In such Figure 3 The system shown is used in the experiment, and the structure and parameters of the reactor in the system are as follows: Figures 1-2 As shown, the membrane separator structure is as follows: Figure 4As shown, specifically, the pore size distribution on the tube wall is 3-5 μm; the spacing between the pores on the tube wall is 10 μm; the tube wall thickness is 100 μm; the porosity of the tube wall is 40%; the tube is a circular tube with a diameter of 3 mm; the number of tubes is 37 or 61, this embodiment uses 37 tubes with a tube spacing of 7.5 mm; the ratio of the total cross-sectional area of ​​the tubes to the cross-sectional area of ​​the shell is 0.093; the shell is cylindrical, with a length of 270 mm and a diameter of 60 mm; the shortest distance between the tubes and the shell is 6 mm; baffles are arranged in the space formed by the shell and the tube wall, with a distance of 30 mm between adjacent baffles; the membrane separation uses a silicon oxide membrane with a pore size distribution range of 0.8-1 nm; the membrane thickness is 10 μm; and the porosity is 20%.

[0064] Add 3 mmol of PdCl2, 0.5 mmol of tri-n-butylphosphine (P(t-Bu)3), 4 mmol of toluenesulfonic acid, and 100 mL of anhydrous methanol to the catalyst tank, and mix thoroughly with a stirrer. Add 250 mL of dicyclopentadiene to the cyclic olefin tank and 1 L of methanol to the methanol tank. Purify the reaction apparatus three times with carbon monoxide. Using a pump, pump the catalyst, cyclopentadiene, and methanol into the mixer at flow rates of 5 mL / h, 100 mL / h, and 400 mL / h, respectively. After thorough mixing, introduce the mixture into the microbubble reactor. Then, introduce carbon monoxide into the tube bundle of the microbubble reactor and gradually increase the pressure to 5.0 MPa. The temperature is slowly increased to 70°C. The reaction product is fed into a membrane separation unit for separation, while carbon monoxide is introduced as a carrier gas to blow out the precipitated product on the permeate side of the membrane separator. The membrane rejection rate is 40%. The catalyst-free permeate is sent to a product collection tank, and the gas removed is sent to a waste gas treatment tank. The catalyst-containing non-permeate is recycled back to the reactor. Unreacted gaseous feedstock is recycled back to the gas source, i.e., the gas phase storage tank, for pressurization. After the reaction is complete, a sample is taken from the product collection tank and quantitatively analyzed by gas chromatography. The product contains no catalyst, the conversion rate of dicyclopentadiene is 99%, and the selectivity of dicyclopentadienoate is 98%.

[0065] Example 3

[0066] In such Figure 3 The system shown is used in the experiment, and the structure and parameters of the reactor in the system are as follows: Figures 1-2 As shown, the membrane separator structure is as follows: Figure 4As shown, specifically, the pore size distribution on the tube wall is 3-5 μm; the spacing between the pores on the tube wall is 10 μm; the tube wall thickness is 100 μm; the porosity of the tube wall is 40%; the tube is a circular tube with a diameter of 3 mm; the number of tubes is 37 or 61, this embodiment uses 37 tubes with a tube spacing of 7.5 mm; the ratio of the total cross-sectional area of ​​the tubes to the cross-sectional area of ​​the shell is 0.093; the shell is cylindrical, with a length of 270 mm and a diameter of 60 mm; the shortest distance between the tubes and the shell is 6 mm; baffles are arranged in the space formed by the shell and the tube wall, with a distance of 30 mm between adjacent baffles; the membrane separation uses a silicon oxide membrane with a pore size distribution range of 0.8-1 nm; the membrane thickness is 10 μm; and the porosity is 20%.

[0067] Add 1.5 mmol of bis(triphenylphosphine)palladium dichloride (PdCl2(PPh3)2), 0.5 mmol of tricyclohexylphosphine (PCy3), 1 mmol of sulfuric acid, and 100 mL of anhydrous methanol to the catalyst tank, and mix thoroughly with a stirrer. Add 400 mL of cyclopentene to the cyclic olefin tank and 800 mL of methanol to the methanol tank. Purify the reaction apparatus three times with carbon monoxide. Use a pump to pump the catalyst, cyclopentene, and methanol into the mixer at flow rates of 5 mL / h, 100 mL / h, and 200 mL / h, respectively. After thorough mixing, introduce the mixture into the microbubble reactor. Then, introduce carbon monoxide into the tube bundle of the microbubble reactor and gradually increase the pressure to 4.0 MPa. The temperature is slowly increased to 100℃, and the reaction product stream is fed into a membrane separation unit for separation. Simultaneously, carbon monoxide is introduced as a carrier gas to blow out the precipitated product from the permeate side of the membrane separator. The membrane rejection rate is 40%. The catalyst-free permeate is sent to a product collection tank, while the gas removed is sent to a waste gas treatment tank. The catalyst-containing non-permeate is recycled back to the reactor. Unreacted gaseous feedstock is recycled back to the gas source, i.e., the gas phase storage tank, for pressurization. After the reaction is complete, a sample is taken from the product collection tank and quantitatively analyzed using gas chromatography. The product contains no catalyst, the cyclopentene conversion rate is 99%, and the selectivity of methyl cyclopentanoate is 98%.

[0068] Example 4

[0069] Same as Example 1, except that the amount of PPh3 added to the catalyst tank is 0.25 mmol.

[0070] Reaction results: Cyclopentadiene conversion rate was 95%, and dimethyl cyclopentanoate selectivity was 96%.

[0071] Example 5

[0072] Same as Example 1, except that the amount of PPh3 added to the catalyst tank is 0.1 mmol.

[0073] Reaction results: Cyclopentadiene conversion rate was 93%, and dimethyl cyclopentanoate selectivity was 90%.

[0074] Example 6

[0075] Similar to Example 1, except that the cyclic olefin is norbornene, which is introduced into the tube bundle of the microbubble reactor with carbon monoxide and the pressure is gradually increased to 1.0 MPa.

[0076] Reaction results: The conversion rate of norbornene was 92%, and the selectivity of the product dimethyl norbornene was 90%.

[0077] Example 7

[0078] Same as Example 1, except that 100 mL of cyclopentadiene was added to the cycloolefin tank and 800 mL of methanol was added to the methanol tank. The reaction apparatus was purged three times with carbon monoxide, and the catalyst, dicyclopentadiene, and methanol were pumped into the mixer at flow rates of 5 mL / h, 100 mL / h, and 800 mL / h, respectively.

[0079] Reaction results: The conversion rate of cyclopentadiene was 90%, and the selectivity of the product dimethyl cyclopentanoate was 88%.

[0080] Example 8

[0081] Similar to Example 1, except that the temperature is controlled to rise slowly to 140°C.

[0082] Reaction results: Cyclopentadiene conversion rate was 95%, and dimethyl cyclopentanoate selectivity was 94%.

[0083] Example 9

[0084] Similar to Example 1, except that the pore size distribution of the tube wall is 5-10 μm, the porosity remains unchanged, and the spacing and number of pores are adjusted accordingly.

[0085] Reaction results: The conversion rate of cyclopentadiene was 91%, and the selectivity of dimethyl cyclopentadiate was 90%.

[0086] Comparative Example 1

[0087] Similar to Example 1, except that an AC250 automatic reactor was used for the reaction.

[0088] Reaction results: The conversion rate of cyclopentadiene was 80%, and the selectivity of dimethyl cyclopentadiate was 88%.

[0089] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for carbonylating cycloolefins, characterized in that, The method is carried out in an apparatus comprising a shell-and-tube reactor, the shell-and-tube reactor comprising: The shell, and a tube located inside and penetrating the shell, the tube wall having holes for the passage of a limited gaseous material; The tube passing through both ends of the shell has a gaseous raw material inlet and an unreacted gaseous raw material outlet, and the shell has a liquid raw material inlet and a product outlet; The method includes: feeding a solution containing a catalyst and cyclic olefins into the shell side of a reactor, feeding a gas phase containing CO into the tube side of the reactor, and allowing some CO to enter the tube side through pores in the tube wall and react with the solution containing the catalyst and cyclic olefins.

2. The synthesis method according to claim 1, wherein, The pore size distribution range of the holes on the pipe wall is 2-10 μm, preferably 3-5 μm; and / or The spacing between the holes in the tube wall is 5-30 μm, preferably 10-20 μm; and / or The thickness of the tube wall is 20-200 μm, preferably 50-100 μm; and / or The porosity of the tube wall is 20-50%, preferably 30-40%.

3. The synthesis method according to claim 1 or 2, wherein, The cyclic olefin is a cyclic olefin with 5-20 carbon atoms, preferably 5-12 carbon atoms, and is preferably at least one of cyclopentadiene, dicyclopentadiene, norbornene, and norbornadiene.

4. The method according to any one of claims 1-3, wherein, The conditions for the contact reaction include: CO gas pressure 1.0-10.0 MPa, preferably 2-5 MPa; and / or The reaction temperature is 50-160℃, preferably 70-110℃.

5. The method according to any one of claims 1-4, wherein, The catalyst is a metal ion-phosphonic acid catalyst, wherein the metal ion is a Group VIII and / or IIB metal, preferably. The metal ion is at least one selected from Pd, Rh, Ni, Co, and Cu, preferably Pd; and / or The molar ratio of acid, phosphine, and palladium in the catalyst is 0.1-5:1:1-10, preferably 0.5-2:1:1-6.

6. The method according to claim 5, wherein, The acid is at least one selected from the following: toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, sulfuric acid, trifluoroacetic acid, sodium phosphate, and hydrochloric acid; and / or The phosphine is at least one selected from triphenylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, 1,2-bis(diphenylphosphine)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphine)butane, bis(diphenylphosphine)ferrocene, 1,3-bis(di-tert-butylphosphine)propane, and 1,2-bis(di-tert-butylphosphine)ethane.

7. The method according to any one of claims 1-6, wherein, In the solution containing the catalyst and cyclic olefins, The volume ratio of catalyst to solvent is 1:20-80, and the catalyst is a solution containing palladium-phosphonic acid catalyst with a concentration of 5-30 mmol / L (calculated as palladium); and / or The volume ratio of the cyclic olefin to the solvent is 1:0.5-8, preferably 1:0.5-4; Preferably, the solvent is a C1-C8 alcohol solvent, and more preferably methanol.

8. The method according to any one of claims 1-7, wherein, The method further includes: passing the catalyst-containing product stream after the contact reaction into a membrane separator for membrane separation to obtain a permeate product and a catalyst-containing non-permeate stream, and recycling the catalyst-containing non-permeate stream back into a solution containing the catalyst and cyclic olefins.

9. The method according to claim 8, wherein, The membrane used for membrane separation is selected from at least one of carbon nanotubes, silica membranes, NaA zeolite membranes, and ZSM-5 zeolite membranes, with silica membranes being preferred.

10. The method according to claim 8 or 9, wherein, The membrane used for membrane separation has a pore size distribution range of 0.5-2 nm, preferably 0.8-1 nm, and / or a membrane thickness of 2-20 μm, preferably 5-10 μm, and / or a porosity of 10-40%, preferably 15-25%.

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