Method for producing target product using membrane reactor

Abstract

To provide a membrane reactor capable of improving yield of a target product by progressing efficiently a catalyst reaction, in a reaction controlled by chemical equilibrium.SOLUTION: Concerning a membrane reactor for performing a reaction controlled by chemical equilibrium, the membrane reactor has a separation membrane for selectively and continuously separating, from reaction liquid, a by-product generated by the reaction. By selectively and continuously separating the by-product from the reaction liquid, the chemical equilibrium is shifted and the reaction is furthermore progressed.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a reactor that continuously separates by-products produced in a reaction governed by chemical equilibrium, shifts the chemical equilibrium, and improves the yield of a target product, and in particular, to a membrane reactor equipped with a separation membrane that selectively separates and removes by-products. [Background technology]

[0002] By integrating a catalytic reactor with a separator, the yield of the target product can be improved by separating and removing reaction by-products. Conventionally, distillation and adsorption have been used as separation methods, but these have problems such as high energy consumption, low separation efficiency, and discontinuous operation. For example, reactive distillation, which combines a reactor and a distillation column, is known and has been applied to esterification reactions, in which an acid and an alcohol are reacted and water is separated to produce an ester. However, distillation is affected by azeotropy, so the water separation performance is low, resulting in limited yields of the target product. Another issue with distillation is the high energy consumption. Reactive distillation has also been applied to reactions that produce methanol as a by-product. For example, a reaction has been studied in which methyl acetate and 2-propanol are reacted, the methanol is separated, and an alcohol-exchanged ester is produced (Non-Patent Document 1). However, when a transesterification reaction is carried out by reactive distillation, the boiling points of the by-product methanol and the reaction raw material methyl acetate are close, so not only methanol but also the raw material methyl acetate are removed from the reactor, which limits the improvement in the yield of the target product. In other words, the problem with reactive distillation is that it is an energy-intensive process and has low separation ability for the by-product to be removed.

[0003] A method has also been used in which a catalytic reaction vessel is equipped with an adsorbent, and by-products are adsorbed onto the adsorbent to promote the reaction. Examples of adsorbents include ionic liquids and molecular sieves 3A and 5A, which have been used in gas-phase methanol synthesis and transesterification reactions (Patent Document 1, Non-Patent Document 2). The adsorbent adsorbs the by-products, such as methanol and water, reducing the apparent concentration of the by-products in the reaction fluid and improving the yield of the target product. A key feature of methods using adsorbents is their high separation performance for by-products. However, they require regeneration of the adsorbent to desorb the adsorbed water and methanol. In other words, the challenge with adsorption methods is that they cannot be operated continuously.

[0004] Since around 2000, research has been progressing on membrane reactors that combine a reaction vessel with a separation membrane, and to date, studies have been conducted on reactions to synthesize esters from carboxylic acids and alcohols (Patent Document 2, Non-Patent Documents 3-5). Separation membranes are characterized by an energy-saving process that allows for continuous operation, and by their particularly high separation ability for water. However, there have been no reports of selectively separating organic substances such as methanol from non-aqueous organic mixed liquids to promote catalytic reactions. Patent Document 3 invents a method for selectively separating methanol from non-aqueous organic mixed liquids, but its application to membrane reactors has not been studied. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2018-526203 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-47213 [Patent Document 3] Japanese Patent Application Laid-Open No. 2011-51975 [Non-patent literature]

[0006] [Non-Patent Document 1] Lanlan Shen, Lei Wang, Hui Wan, Guofeng Guan, Ind. Eng. Chem. Res., 2014, 53, 3827-3833 [Non-patent document 2] M. Hatano, Y. Tabata, Y. Yoshida, K. Toh, K. Yamashita, Y. Ogura, K. Ishihara, Green Chem., 2018, 20, 1193 [Non-patent document 3] K. Tanaka, R. Yoshikawa, C. Ying, H. Kita, K. Okamoto, Catal. Today, 2001, 67, 121-125. [Non-patent document 4] Y. Hasegawa, C. Abe, F. Mizukami, Y. Kowata, T. Hanaoka, J. Memb. Sci., 2012, 415-416, 368-374. [Non-patent document 5] M.-H. Zhu, Z.-J. Feng, X.-M. Hua, H. Hu, S.-L. Xia, N. Hu, Z. Yang, I. Kumakiri, XS Chen, H. Kita, Microporous Mesoporous Mater., 2016, 233, 171-176. Summary of the Invention [Problem to be solved by the invention]

[0007] The object of the present invention is to provide a membrane reactor which can solve the problems of the above-mentioned conventional techniques, such as high energy consumption, low separation performance, and discontinuous operation, and can efficiently proceed with catalytic reactions to improve the yield of the target product. [Means for solving the problem]

[0008] The present invention relates to a separation-type reactor that efficiently and continuously advances a catalytic reaction and a method for producing a target product using the same, and more particularly to a membrane reactor that uses a separation membrane as a means for overcoming the problems of conventional techniques such as distillation and adsorption, such as high energy consumption, low separation ability, or discontinuous operation. That is, the present invention includes the following aspects: In one aspect, the present invention comprises: [1] A membrane reactor for carrying out a reaction governed by chemical equilibrium, The membrane reactor is provided with a separation membrane that selectively separates by-products generated by the reaction from the reaction liquid, The present invention relates to a membrane reactor in which the by-products are selectively and continuously separated from the reaction liquid, thereby shifting the chemical equilibrium in the reaction and allowing the reaction to proceed further. Here, in one embodiment of the membrane reactor of the present invention, [2] The membrane reactor according to [1] above, The by-product is methanol, and the separation membrane is an inorganic membrane that selectively separates methanol. In one embodiment, the membrane reactor of the present invention comprises: [3] The membrane reactor according to [1] or [2] above, The separation membrane is characterized in that it is a zeolite membrane. In one embodiment, the membrane reactor of the present invention comprises: [4] The membrane reactor according to [3] above, The separation membrane FAU The membrane is characterized by being formed by depositing a type zeolite on a porous support. In one embodiment, the membrane reactor of the present invention comprises: [5] The membrane reactor according to any one of [1] to [4] above, The reactor is characterized by further comprising at least one selected from the group consisting of a supply section for supplying reaction raw materials or a catalyst, a recovery section for recovering by-products separated by the separation membrane, a discharge section for discharging a reaction liquid containing the target product, and a catalyst recovery section for recovering the catalyst. In another aspect, the present invention provides [6] A method for producing a product produced by a reaction governed by chemical equilibrium, comprising: The present invention relates to a production method, comprising a step of reacting reaction raw materials in the presence of a catalyst in the membrane reactor according to any one of the above [1] to [5] to produce the product and by-products, and a step of selectively and continuously separating the by-products from the reaction liquid by a separation membrane of the membrane reactor. Here, in one embodiment, the manufacturing method of the present invention includes: [7] The manufacturing method according to [6] above, The reaction governed by chemical equilibrium is characterized in that the conversion rate does not reach 100% due to the presence of the by-products. In one embodiment, the manufacturing method of the present invention includes: [8] The manufacturing method according to [6] or [7] above, The reaction governed by chemical equilibrium is an esterification reaction or a transesterification reaction. In one embodiment, the manufacturing method of the present invention includes: [9] The manufacturing method according to any one of [6] to [8] above, The reaction liquid is a non-aqueous mixed solution. In one embodiment, the manufacturing method of the present invention includes:

[10] The manufacturing method according to any one of [6] to [9] above, supplying reaction raw materials and / or catalyst to the reaction vessel; recovering the reaction solution containing the target product; The present invention is characterized in that it further comprises: [Effects of the Invention]

[0009] The membrane reactor according to the present invention can continuously and selectively separate and discharge the by-products produced in the catalytic reaction out of the system, thereby shifting the chemical equilibrium and further promoting the reaction, thereby increasing the yield of the target product. Thus, the membrane reactor according to the present invention can continuously produce the target product while saving energy and resources. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 shows a schematic diagram of a batch-type membrane reactor according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011] The membrane reactor according to the present invention is a membrane reactor for carrying out a reaction governed by chemical equilibrium, and is equipped with a separation membrane that selectively separates by-products generated by the reaction from the reaction solution. The separation membrane can be installed inside the membrane reactor. The separation membrane may be installed so as to be in direct contact with the reaction solution, or so as not to be in contact with the reaction solution. This allows the by-products to be selectively and continuously separated from the reaction solution, shifting the chemical equilibrium of the reaction and allowing the reaction to proceed further. The specific form of the membrane reactor according to the present invention is not limited as long as it can selectively and continuously separate by-products from the reaction solution using a separation membrane and can improve the yield of the target product. For example, a batch type, a continuous tank type, a continuous flow type, or the like can be adopted.

[0012] FIG. 1 is a schematic diagram showing one embodiment of a batch-type membrane reactor according to the present invention. In FIG. 1, this membrane reactor comprises a reaction vessel 1 and a separation membrane 2 installed in the reaction vessel 1. A rotary pump 3 is installed on the permeation side of the separation membrane 2 as a suction means. The separation membrane 2 and the rotary pump 3 constitute a separation section. The separation membrane may also be equipped with a recovery section for recovering the by-product liquid or vapor that permeates the separation membrane. In FIG. 1, a recovery section equipped with a trap tube 8, a Dewar vessel 9, a switching valve 10, and the like is installed between the separation membrane 2 and the rotary pump 3 to recover the liquid or vapor that permeates the separation membrane. The separation membrane may be an integrated type incorporated into the reaction vessel, or a separate separation vessel equipped with the separation membrane may be installed separately from the reaction vessel, and the separation vessel and the reaction vessel may be connected by piping. When a separate separation vessel is installed, a cooling section may be installed in the piping between the reaction vessel and the separation vessel. The cooling section may be directly connected to the reaction vessel 1, as with the cooler 6 shown in FIG. 1. The reaction vessel 1 may be provided with a stirring means such as a stirring bar 4 and a magnetic stirrer 5, or with a stirrer. The reaction vessel 1 may also be equipped with an electric furnace 7. In the case of a continuous flow system, the reaction vessel 1 may also be provided with a supply section comprising a liquid transfer pump and piping for supplying reaction raw materials, a recovery section for recovering by-products that have permeated the separation membrane, a discharge section comprising a liquid transfer pump and piping for discharging the reaction solution, or a catalyst recovery section for recovering the catalyst.

[0013] In the present invention, the type of separation membrane is not particularly limited, as long as it is stable under catalytic reaction conditions and can selectively remove by-products from a mixture of the reaction raw materials and the target reaction product. Separation membranes with excellent properties for separating by-products include 1) membranes that selectively permeate and separate by-products and 2) membranes that selectively permeate and separate substances other than by-products. In the present invention, it is important to use the membrane that selectively permeates and separates by-products (1). Specifically, the separation membrane to be used can be selected by comprehensively judging the reaction conditions, the shape of the reactor, etc. For industrial implementation, it is required that the membrane has excellent durability, excellent chemical resistance against the reaction solution containing acidic substances that may be generated depending on the reaction conditions and alkaline substances supplied to the system to neutralize the acidic substances, and the like, and that it has sufficient mechanical strength to withstand the mixing of the three phases of gas, liquid, and solid, in that order. Therefore, inorganic membranes that generally have high limit temperatures for use and high chemical resistance are preferred. The type of the inorganic membrane is not particularly limited, but a thin film having pores and affinity for by-products is preferred, and examples thereof include inorganic porous separation membranes such as zeolite membranes, silica membranes, carbon membranes, etc. More preferred are inorganic porous separation membranes with pore diameters in the range of 0.3 to 1 nanometer. The inorganic porous separation membrane is not particularly limited as long as it can selectively remove by-products such as water and methanol from a mixture of reaction raw materials and the target product, and the concentrations of water and methanol removed by permeating the membrane are greater than the concentrations of the by-products in the reaction system. In reactions that produce water as a by-product, a water-selective permeable membrane can be used, such as a separation membrane in which LTA-type zeolite, T-type zeolite, CHA-type zeolite, MFI-type zeolite, FAU-type zeolite, or MOR-type zeolite is deposited on a porous support, a silica membrane, or a carbon membrane. In a reaction that produces methanol as a by-product, a methanol permselective membrane can be used, such as FAU-type zeolite, a carbon membrane, a silica membrane, etc. From the viewpoint of separating methanol from the reaction solution, the Si / Al ratio of the zeolite membrane (the Si / Al atomic ratio in the crystalline framework) is preferably in the range of 1.0 to 3.0, more preferably in the range of 1.0 to 2.2.

[0014] In the present invention, separation membranes include freestanding membranes without a support and separation membranes in which a separation layer is formed on a porous support. There are no particular limitations on whether the separation membrane provided in reactor 1 has a support, but the porous support used to form the separation membrane may be a porous material made of ceramics such as alumina, silica, zirconia, silicon nitride, silicon carbide, etc.; metals such as aluminum, silver, stainless steel, etc.; or organic polymers such as polyethylene, polypropylene, polytetrafluoroethylene, polysulfone, polyimide, etc.

[0015] The shape of the porous support is not particularly limited, and may be tubular, plate-like, or the like. Commercially available tubular supports having an outer diameter of 1 to 200 mm and a length of 1 to 200 cm, and plate-like supports having an outer diameter of approximately 8 to 20 mm and a thickness of 0.2 to several mm, etc., can be used.

[0016] Examples of separation membranes for removing by-products include inorganic porous separation membranes such as zeolite membranes, silica membranes, and carbon membranes formed on the porous support. For example, a method for forming a zeolite membrane is to add a mixed aqueous solution containing zeolite raw materials, such as a silicon source, an aluminum source, an alkali source, and an organic structure-directing agent, and a porous support to a pressure vessel and heat the mixture. Examples of silicon sources that can be used include water glass, colloidal silica, silica powder, and alkoxysilanes. Examples of aluminum sources that can be used include alkoxides such as sodium aluminate, aluminum hydroxide, and aluminum isopropoxide. Examples of alkali sources include hydroxides such as sodium hydroxide and potassium hydroxide.

[0017] The zeolite membranes thus obtained can be used very effectively for the separation of liquid or gas mixtures by pervaporation (PV) or vapor permeation (VP). Pervaporation (PV) is a type of membrane separation in which water is selectively taken up from a mixed solution of water and a solvent, such as alcohol, on the primary side and released as vaporized water vapor on the secondary side. Vapor permeation (VP) is a type of membrane separation in which water vapor is taken up from a mixed vapor of water vapor and solvent vapor on the primary side and released on the secondary side.

[0018] In the present invention, the chemical reaction may be any reaction whose progress is restricted by chemical equilibrium, such as an esterification reaction, an amidation reaction, an ester exchange reaction, etc. Preferably, the by-product is a liquid under standard conditions, and more preferably, an organic compound having less than 10 carbon atoms is used. Examples of reactions that by-produce water include esterification reactions and amidation reactions. For example, in esterification reactions, for example, formic acid, acetic acid, propionic acid, butyric acid, lauric acid, palmitic acid, oleic acid, etc. are used as organic acids, and for example, acetic acid, hydrochloric acid, sulfuric acid, etc. are used as inorganic acids. Furthermore, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutyl alcohol, etc. are used as alcohols. Acetone can also be used instead of alcohol. For example, in amidation reactions, for example, formic acid, acetic acid, etc. are used as carboxylic acids, while ammonia, etc. are used as amines. Examples of reactions that produce methanol as a by-product include transesterification. Examples of methyl esters that can be used include methyl acetate, methyl propionate, methyl butanoate, methyl hexanoate, and methyl acrylate. Examples of alcohols that can be used include ethanol, 1-propanol, 2-propanol, 1-butanol, isobutyl alcohol, 1-pentanol, and 1-hexanol. Phenols can also be used instead of alcohols. Regarding the temperature for removing water and methanol, a high temperature is advantageous from the viewpoint of the permeation rate of water and methanol, and a low temperature is advantageous from the viewpoint of the separation performance of water and methanol, and the temperature can be selected in the range of room temperature to 200° C. When a separation membrane is provided in the reaction vessel, the reaction temperature is selected in the range of 40 to 180° C., preferably in the range of 60 to 120° C. In principle, the operating pressure for separating water or methanol can be set so that a pressure difference occurs on both sides of the membrane, and the membrane pressure is set in the range of 50 to 20,000 Pa. The initial mixing ratio of the reaction substrates can be set as close to molar equivalent as possible. For example, in the transesterification reaction of methyl acetate and 2-propanol, the molar ratio of methyl acetate / 2-propanol can be selected from a wide range, such as from 10 / 1 to 1 / 1000, but is generally selected from a range of 4 / 1 to 1 / 50. Furthermore, in the present invention, a sufficiently high conversion rate of methyl acetate can be achieved even in a range of 2 / 1 to 1 / 4, where the methyl ester concentration is high.

[0019] In the present invention, any catalyst may be used as long as it can promote the chemical reaction, and homogeneous catalysts such as inorganic acids such as hydrochloric acid and sulfuric acid, and metal complex catalysts, as well as heterogeneous catalysts having acid sites such as ion exchange resins and zeolites, are usable. The catalyst concentration can be varied depending on the type of reaction raw material, the catalyst composition and preparation method, reaction conditions, etc., but is usually added in the range of 0.01 to 20% based on the weight of the reaction substrate. For example, in the case of transesterification, it is preferable to add the catalyst in the range of 1 to 10%.

[0020] As used herein, selective separation of by-products refers to selectively separating only the by-products from the reaction raw materials, catalyst, and / or product in the reaction solution using a separation membrane. Furthermore, as used herein, continuous separation of by-products refers to constantly separating the by-products rather than intermittently during the reaction. The by-products separated from the reaction solution by the separation membrane may be one type or two or more types. When multiple by-products are to be separated, multiple configurations such as separation membranes, separation sections, or recovery sections can be appropriately employed.

[0021] As used herein, the phrase "a shift in chemical equilibrium in a reaction causes the reaction to proceed further" means that the removal of by-products from a reaction solution in a chemical equilibrium state shifts the equilibrium toward increasing the amount of the decreased by-products, i.e., toward the production of the target product. As a result, by separating the by-products, the reaction can proceed beyond the conversion rate in a chemical equilibrium state without a separation membrane.

[0022] The present invention will be explained below using specific examples, but the present invention is not limited to these examples in any way. [Example]

[0023] Example 1 In this invention, FAU zeolite membrane A was prepared on the outer surface of a porous α-alumina tube using a hydrothermal synthesis method. Sodium aluminate, sodium hydroxide, water glass, and ion-exchanged water were mixed to prepare a membrane synthesis aqueous solution. The molar composition was 25SiO2:1Al2O3:22Na2O:990H2O. To serve as crystal growth nuclei, Y-type zeolite powder (Tosoh HSZ-320NAA) was rubbed into the outer surface of a porous α-alumina tube (outer diameter 3.0 mm, inner diameter 2.0 mm, average pore size 0.3 μm, porosity 50%). The tube was then placed in an autoclave together with the synthesis aqueous solution and heated at 100°C for 5 hours. After synthesis, the alumina tube was cooled to room temperature, removed from the autoclave, washed with ion-exchanged water until the pH of the wash water was less than 9, and dried overnight at room temperature to obtain FAU zeolite membrane A.

[0024] The separation performance of FAU-type zeolite membrane A was evaluated in a PV test (liquid temperature 75°C) using a 90 wt% 2-propanol aqueous solution. One side of the zeolite membrane was connected to a stainless steel tube using epoxy resin, and the other side was sealed. The zeolite membrane was immersed in the 2-propanol aqueous solution, and the inner surface of the zeolite membrane was depressurized using a rotary pump. Furthermore, helium was supplied as a reference gas at 6.0 mL / min to the surface without the zeolite membrane. The gas composition of the components that permeated the zeolite membrane was analyzed using a mass spectrometer, and the permeation flux and separation factor were determined. As a result, the water permeation flux of FAU-type zeolite membrane A was 0.16 mol / m 2 / s, and the separation factor was 586. In addition, in a PV test using a 10 wt% methanol / 2-propanol mixture (liquid temperature 80°C), the methanol permeation flux was 6.1 mmol / m 2 / s, and the methanol / 2-propanol separation factor was 5.

[0025] A transesterification reaction was carried out using a cation exchange resin (Dowex 50Wx2 200-400, H-type, Wako) as a catalyst and an FAU-type zeolite membrane as an organic permselective separation membrane. The cation exchange resin was mixed with 2-propanol in an amount twice its weight, shaken for 30 minutes, and then collected by suction filtration. The resin was subjected to the same procedure two or three times, dried under reduced pressure, and used as a catalyst.

[0026] A solution of methanol, 2-propanol, methyl acetate, and isopropyl acetate mixed in a molar ratio of 1:2:2:1 was poured into the reactor, and 3 g of a cation exchange catalyst resin was added to the mixed solution as a catalyst. A separation membrane 2, in which FAU zeolite, a by-product with selective permeability to methanol, was deposited on a porous support, was placed in the reactor 1, and the inside of the membrane was suctioned with a rotary pump. The electric furnace temperature was set to 80°C, and a transesterification reaction was carried out while methanol was continuously separated by vapor permeation through the separation membrane.

[0027] After the reaction, the solution was weighed and its composition was analyzed by gas chromatography (TCD, GC-2014, Shimadzu Corporation, column: Porapak-Q, TCD temperature: 250°C, column temperature: 150-230°C). The yield was calculated as isopropyl acetate / (methyl acetate + isopropyl acetate) × 100.

[0028] After 16 hours of reaction, the solution contained 0.12 mol of methyl acetate, 0.12 mol of 2-propanol, 0.03 mol of methanol, and 0.16 mol of isopropyl acetate, giving a yield of 57%.

[0029] (Comparative Example 1) A transesterification reaction was carried out in the same manner as in Example 1, except that the separation membrane 2 was not used. A solution containing 0.3 mol of methyl acetate and 0.3 mol of 2-propanol was placed in a reaction vessel, and 3 g of a cation exchange catalyst resin was added to the mixed solution as a transesterification reaction catalyst to cause an esterification reaction.

[0030] After 16 hours of reaction, the solution contained 0.18 mol of methyl acetate, 0.18 mol of 2-propanol, 0.09 mol of methanol, and 0.11 mol of isopropyl acetate, giving a yield of 38%.

[0031] The results of Comparative Example 1 show that the yield of isopropyl acetate at equilibrium was 38% when the catalytic reaction was carried out alone. However, by continuously removing the by-product methanol from the reaction system using a separation membrane, the yield of isopropyl acetate was increased to 57% (Example 1). This indicates that by selectively separating the by-product methanol in the transesterification reaction, the chemical equilibrium can be manipulated to efficiently produce the target product.

[0032] There have been no examples of membrane reactors being used in chemical equilibrium reactions where the by-products are organic. In other words, this invention is the first example in the world to demonstrate that the target product can be efficiently produced by separating and removing by-products using a separation membrane and manipulating the chemical equilibrium.

[0033] Example 2 FAU-type zeolite membrane B was prepared on the outer surface of a porous α-alumina tube using hydrothermal synthesis. A membrane synthesis solution was prepared by mixing sodium aluminate, sodium hydroxide, water glass, and ion-exchanged water. The molar composition was 5SiO2:1Al2O3:7.5Na2O:375H2O. Y-type zeolite powder (Tosoh HSZ-320NAA) was rubbed onto the outer surface of the porous α-alumina tube (outer diameter 3.0 mm, inner diameter 2.0 mm, average pore size 0.3 μm, porosity 50%) as a nucleus for crystal growth. The tube was then placed in an autoclave with the synthesis solution and heated at 90°C for 18 hours. After synthesis, the alumina tube was cooled to room temperature, removed from the autoclave, washed with ion-exchanged water until the pH of the wash water was less than 9, and dried overnight at room temperature to obtain FAU-type zeolite membrane B.

[0034] The separation performance of the FAU-type zeolite membrane B was evaluated in the same manner as in Example 1, except that the FAU-type zeolite membrane B was used. The water permeation flux was 0.17 mol / m 2 / s, and the separation factor was 568. In addition, in a PV test using a 10 wt% methanol / 2-propanol mixture (liquid temperature 80°C), the methanol permeation flux was 6.4 mmol / m 2 / s, and the methanol / 2-propanol separation factor was 13.

[0035] The water permeation flux and separation factor were comparable to those of the FAU zeolite membrane A in Example 1. On the other hand, the methanol / 2-propanol separation factor of the FAU zeolite membrane B was high.

[0036] A transesterification reaction was carried out in the same manner as in Example 1, except that a mixed solution of 0.3 mol of methyl acetate and 0.3 mol of 2-propanol was used as the reaction substrate and FAU-type zeolite membrane B was used as the separation membrane 2. As a catalyst, 3 g of a cation exchange resin (Dowex50Wx2 200-400, H-type, Wako) that had been washed two or three times with twice its weight of 2-propanol and dried under reduced pressure was used.

[0037] After 12 hours of reaction, the solution contained 0.17 mol of methyl acetate, 0.17 mol of 2-propanol, 0.08 mol of methanol, and 0.12 mol of isopropyl acetate, giving a yield of 40%.

[0038] Compared to Example 1, in Example 2, no methanol was present at the initial stage of the reaction. Nevertheless, the yield was increased compared to Comparative Example 1. This indicates that the by-product methanol was removed by the FAU zeolite membrane, and the chemical equilibrium was manipulated.

[0039] Example 3 A transesterification reaction was carried out in the same manner as in Example 2 above, except that the reaction substrates were 0.30 mol of methyl acetate and 0.30 mol of 1-propanol.

[0040] After 12 hours of reaction, the solution contained 0.13 mol of methyl acetate, 0.15 mol of 1-propanol, 0.15 mol of propyl acetate, and 0.10 mol of methanol, giving a 54% yield of propyl acetate.

[0041] Example 4 A transesterification reaction was carried out in the same manner as in Example 2 above, except that the reaction substrates were 0.27 mol of methyl acetate and 0.27 mol of 1-butanol.

[0042] After 12 hours of reaction, the solution contained 0.11 mol of methyl acetate, 0.12 mol of 1-butanol, 0.15 mol of butyl acetate, and 0.07 mol of methanol, giving a 58% yield of butyl acetate.

[0043] Example 5 A transesterification reaction was carried out in the same manner as in Example 2 above, except that the reaction substrates were 0.25 mol of methyl acetate and 0.25 mol of 1-pentanol.

[0044] After 12 hours of reaction, the solution contained 0.10 mol of methyl acetate, 0.12 mol of 1-pentanol, 0.13 mol of pentyl acetate, and 0.06 mol of methanol, giving a 56% yield of pentyl acetate.

[0045] Example 6 A transesterification reaction was carried out in the same manner as in Example 2 above, except that the reaction substrates were 0.23 mol of methyl acetate and 0.23 mol of 1-hexanol.

[0046] After 12 hours of reaction, the solution contained 0.11 mol of methyl acetate, 0.12 mol of 1-hexal, 0.10 mol of hexyl acetate, and 0.05 mol of methanol, giving a 46% yield of hexyl acetate.

[0047] Example 7 A transesterification reaction was carried out in the same manner as in Example 2 above, except that the reaction substrates were 0.27 mol of methyl propionate and 0.27 mol of 1-propanol.

[0048] After 12 hours of reaction, the solution contained 0.08 mol of methyl propionate, 0.09 mol of 1-propanol, 0.17 mol of propyl propionate, and 0.03 mol of methanol, giving a 66% yield of propyl propionate.

[0049] Example 8 A transesterification reaction was carried out in the same manner as in Example 2 above, except that the reaction substrates were 0.25 mol of methyl propionate and 0.25 mol of 1-butanol.

[0050] After 12 hours of reaction, the solution contained 0.08 mol of methyl propionate, 0.08 mol of 1-butanol, 0.15 mol of butyl propionate, and 0.03 mol of methanol, giving a 65% yield of butyl propionate.

[0051] Example 9 A transesterification reaction was carried out in the same manner as in Example 2 above, except that the reaction substrates were 0.21 mol of methyl propionate and 0.21 mol of 1-hexanol.

[0052] After 12 hours of reaction, the solution contained 0.10 mol of methyl propionate, 0.09 mol of 1-hexal, 0.11 mol of hexyl propionate, and 0.04 mol of methanol, giving a 54% yield of hexyl propionate.

[0053] Example 10 A transesterification reaction was carried out in the same manner as in Example 2 above, except that the reaction substrates were 0.25 mol of methyl butanoate and 0.25 mol of 1-propanol.

[0054] After 12 hours of reaction, the solution contained 0.10 mol of methyl butanoate, 0.09 mol of 1-propanol, 0.15 mol of propyl butanoate, and 0.04 mol of methanol, giving a 62% yield of propyl butanoate.

[0055] Example 11 A transesterification reaction was carried out in the same manner as in Example 2 above, except that the reaction substrates were 0.23 mol of methyl butanoate and 0.23 mol of 1-butanol.

[0056] After 12 hours of reaction, the solution contained 0.08 mol of methyl butanoate, 0.08 mol of 1-butanol, 0.14 mol of butyl butanoate, and 0.03 mol of methanol, giving a 64% yield of butyl butanoate.

[0057] Example 12 A transesterification reaction was carried out in the same manner as in Example 2 above, except that the reaction substrates were 0.21 mol of methyl butanoate and 0.21 mol of 1-pentanol.

[0058] After 12 hours of reaction, the solution contained 0.08 mol of methyl butanoate, 0.09 mol of 1-pentanol, 0.12 mol of pentyl butanoate, and 0.04 mol of methanol, giving a 60% yield of pentyl butanoate.

[0059] Example 13 A transesterification reaction was carried out in the same manner as in Example 2 above, except that the reaction substrates were 0.20 mol of methyl butanoate and 0.20 mol of 1-hexanol.

[0060] After 12 hours of reaction, the solution contained 0.06 mol of methyl butanoate, 0.06 mol of 1-hexanol, 0.13 mol of hexyl butanoate, and 0.03 mol of methanol, giving a 67% yield of hexyl butanoate.

[0061] Example 14 A transesterification reaction was carried out in the same manner as in Example 2 above, except that the reaction substrates were 0.25 mol of methyl butanoate and 0.25 mol of 2-propanol.

[0062] After 12 hours of reaction, the solution contained 0.14 mol of methyl butanoate, 0.13 mol of 2-propanol, 0.11 mol of isopropyl butanoate, and 0.03 mol of methanol, giving a yield of 44% isopropyl butanoate.

[0063] Example 15 A transesterification reaction was carried out in the same manner as in Example 2 above, except that the reaction substrates were 0.21 mol of methyl hexanoate and 0.21 mol of 1-propanol.

[0064] After 12 hours of reaction, the solution contained 0.09 mol of methyl hexanoate, 0.06 mol of 1-propanol, 0.13 mol of propyl hexanoate, and 0.02 mol of methanol, giving a 60% yield of propyl hexanoate.

[0065] Example 16 A transesterification reaction was carried out in the same manner as in Example 2 above, except that the reaction substrates were 0.20 mol of methyl hexanoate and 0.20 mol of 1-butanol.

[0066] After 12 hours of reaction, the solution contained 0.05 mol of methyl hexanoate, 0.04 mol of 1-butanol, 0.14 mol of butyl hexanoate, and 0.01 mol of methanol, giving a 73% yield of butyl hexanoate.

[0067] Example 17 A transesterification reaction was carried out in the same manner as in Example 2 above, except that the reaction substrates were 0.18 mol of methyl hexanoate and 0.18 mol of 1-pentanol.

[0068] After 12 hours of reaction, the solution contained 0.04 mol of methyl hexanoate, 0.03 mol of 1-pentanol, 0.15 mol of pentyl hexanoate, and 0.004 mol of methanol, giving a 78% yield of pentyl hexanoate.

[0069] Example 18 A transesterification reaction was carried out in the same manner as in Example 2 above, except that the reaction substrates were 0.17 mol of methyl hexanoate and 0.17 mol of 1 hexanol.

[0070] After 12 hours of reaction, the solution contained 0.03 mol of methyl hexanoate, 0.03 mol of 1-hexanol, 0.13 mol of hexyl hexanoate, and 0.001 mol of methanol, giving a hexyl hexanoate yield of 80%.

[0071] (Comparative Example 2) A transesterification reaction was carried out in the same manner as in Example 3 above, except that the reaction substrates were 0.30 mol of methyl acetate and 0.30 mol of 1-propanol, and the separation membrane 2 was not used.

[0072] After 16 hours of reaction, the solution contained 0.16 mol of methyl acetate, 0.18 mol of 1-propanol, 0.13 mol of propyl acetate, and 0.14 mol of methanol, giving a 46% yield of propyl acetate.

[0073] (Comparative Example 3) A transesterification reaction was carried out in the same manner as in Example 4 above, except that the reaction substrates were 0.30 mol of methyl acetate and 0.30 mol of 1-butanol, and the separation membrane 2 was not used.

[0074] After 12 hours of reaction, the solution contained 0.14 mol of methyl acetate, 0.20 mol of 1-butanol, 0.12 mol of butyl acetate, and 0.10 mol of methanol, giving a butyl acetate yield of 46%.

[0075] Comparative Example 4 A transesterification reaction was carried out in the same manner as in Example 5 above, except that the reaction substrates were 0.30 mol of methyl acetate and 0.30 mol of 1-pentanol, and the separation membrane 2 was not used.

[0076] After 12 hours of reaction, the solution contained 0.16 mol of methyl acetate, 0.17 mol of 1-pentanol, 0.13 mol of pentyl acetate, and 0.12 mol of methanol, giving a 44% yield of pentyl acetate.

[0077] (Comparative Example 5) A transesterification reaction was carried out in the same manner as in Example 6 above, except that the reaction substrates were 0.30 mol of methyl acetate and 0.30 mol of 1-hexal, and the separation membrane 2 was not used.

[0078] After 12 hours of reaction, the solution contained 0.16 mol of methyl acetate, 0.20 mol of 1-hexal, 0.10 mol of hexyl acetate, and 0.13 mol of methanol, giving a 38% yield of hexyl acetate.

[0079] (Comparative Example 6) A transesterification reaction was carried out in the same manner as in Example 7 above, except that the reaction substrates were 0.30 mol of methyl propionate and 0.30 mol of 1-propanol, and the separation membrane 2 was not used.

[0080] After 12 hours of reaction, the solution contained 0.17 mol of methyl propionate, 0.16 mol of 1-propanol, 0.14 mol of propyl propionate, and 0.12 mol of methanol, giving a 45% yield of propyl propionate.

[0081] (Comparative Example 7) A transesterification reaction was carried out in the same manner as in Example 8 above, except that the reaction substrates were 0.30 mol of methyl propionate and 0.30 mol of 1-butanol, and the separation membrane 2 was not used.

[0082] After 16 hours of reaction, the solution contained 0.18 mol of methyl propionate, 0.18 mol of 1-butanol, 0.12 mol of butyl propionate, and 0.11 mol of methanol, giving a 40% yield of butyl propionate.

[0083] (Comparative Example 8) A transesterification reaction was carried out in the same manner as in Example 9 above, except that the reaction substrates were 0.30 mol of methyl propionate and 0.30 mol of 1-hexal, and the separation membrane 2 was not used.

[0084] After 12 hours of reaction, the solution contained 0.18 mol of methyl propionate, 0.17 mol of 1-hexal, 0.12 mol of hexyl propionate, and 0.13 mol of methanol, giving a 39% yield of hexyl propionate.

[0085] (Comparative Example 9) A transesterification reaction was carried out in the same manner as in Example 10 above, except that the reaction substrates were 0.18 mol of methyl butanoate and 0.17 mol of 1-propanol, and the separation membrane 2 was not used.

[0086] After 12 hours of reaction, the solution contained 0.10 mol of methyl butanoate, 0.10 mol of 1-propanol, 0.13 mol of propyl butanoate, and 0.10 mol of methanol, giving a 41% yield of propyl butanoate.

[0087] (Comparative Example 10) A transesterification reaction was carried out in the same manner as in Example 11 above, except that the reaction substrates were 0.30 mol of methyl butanoate and 0.30 mol of 1-butanol, and the separation membrane 2 was not used.

[0088] After 12 hours of reaction, the solution contained 0.18 mol of methyl butanoate, 0.23 mol of 1-butanol, 0.11 mol of butyl butanoate, and 0.08 mol of methanol, giving a 37% yield of butyl butanoate.

[0089] (Comparative Example 11) A transesterification reaction was carried out in the same manner as in Example 12 above, except that the reaction substrates were 0.30 mol of methyl butanoate and 0.30 mol of 1-pentanol and the separation membrane 2 was not used.

[0090] After 12 hours of reaction, the solution contained 0.18 mol of methyl butanoate, 0.19 mol of 1-pentanol, 0.12 mol of pentyl butanoate, and 0.08 mol of methanol, giving a 39% yield of pentyl butanoate.

[0091] (Comparative Example 12) A transesterification reaction was carried out in the same manner as in Example 13 above, except that the reaction substrates were 0.27 mol of methyl butanoate and 0.27 mol of 1-hexanol, and the separation membrane 2 was not used.

[0092] After 12 hours of reaction, the solution contained 0.17 mol of methyl butanoate, 0.20 mol of 1-hexanol, 0.09 mol of hexyl butanoate, and 0.08 mol of methanol, giving a 34% yield of hexyl butanoate.

[0093] (Comparative Example 13) A transesterification reaction was carried out in the same manner as in Example 14 above, except that the reaction substrates were 0.30 mol of methyl butanoate and 0.30 mol of 2-propanol, and the separation membrane 2 was not used.

[0094] After 12 hours of reaction, the solution contained 0.17 mol of methyl butanoate, 0.18 mol of 2-propanol, 0.12 mol of isopropyl butanoate, and 0.13 mol of methanol, giving a 40% yield of isopropyl butanoate.

[0095] (Comparative Example 14) A transesterification reaction was carried out in the same manner as in Example 15 above, except that the reaction substrates were 0.30 mol of methyl hexanoate and 0.30 mol of 1-propanol and the separation membrane 2 was not used.

[0096] After 12 hours of reaction, the solution contained 0.20 mol of methyl hexanoate, 0.20 mol of 1-propanol, 0.09 mol of propyl hexanoate, and 0.10 mol of methanol, giving a 33% yield of propyl hexanoate.

[0097] (Comparative Example 15) A transesterification reaction was carried out in the same manner as in Example 16 above, except that the reaction substrates were 0.30 mol of methyl hexanoate and 0.30 mol of 1-butanol, and the separation membrane 2 was not used.

[0098] After 12 hours of reaction, the solution contained 0.15 mol of methyl hexanoate, 0.19 mol of 1-butanol, 0.13 mol of butyl hexanoate, and 0.11 mol of methanol, giving a 46% yield of butyl hexanoate.

[0099] (Comparative Example 16) A transesterification reaction was carried out in the same manner as in Example 17 above, except that the reaction substrates were 0.30 mol of methyl hexanoate and 0.30 mol of 1-pentanol and the separation membrane 2 was not used.

[0100] After 12 hours of reaction, the solution contained 0.16 mol of methyl hexanoate, 0.16 mol of 1-pentanol, 0.14 mol of pentyl hexanoate, and 0.11 mol of methanol, giving a 46% yield of pentyl hexanoate.

[0101] (Comparative Example 17) A transesterification reaction was carried out in the same manner as in Example 18, except that the separation membrane 2 was not used.

[0102] After 12 hours of reaction, the solution contained 0.08 mol of methyl hexanoate, 0.07 mol of 1-hexanol, 0.09 mol of hexyl hexanoate, and 0.10 mol of methanol, giving a 55% yield of hexyl hexanoate.

[0103] Table 1 shows the test results for Examples 1 to 18 and Comparative Examples 1 to 17.

[0104] [Table 1A] [Table 1B] [Table 1C]

[0105] In all 18 types of transesterification reactions, the use of FAU zeolite membranes improved the yield of the target esters, demonstrating that the removal of by-product alcohols using FAU zeolite membranes is effective for the efficient production of various transesterification reactions.

[0106] Next, the effect of reaction temperature was examined in the transesterification reaction using methyl hexanoate and 1-hexanol as reaction substrates.

[0107] Example 20 The transesterification reaction was carried out in the same manner as in Example 18, except that the electric furnace temperature was set to 60°C.

[0108] After 12 hours of reaction, the solution contained 0.06 mol of methyl hexanoate, 0.06 mol of 1-hexanol, 0.11 mol of hexyl hexanoate, and 0.02 mol of methanol, giving a yield of 63%.

[0109] Example 21 The transesterification reaction was carried out in the same manner as in Example 18, except that the electric furnace temperature was 100°C.

[0110] After 12 hours of reaction, the solution contained 0.03 mol of methyl hexanoate, 0.01 mol of 1-hexanol, 0.15 mol of hexyl hexanoate, and 0.01 mol of methanol, giving a yield of 82%.

[0111] (Comparative Example 19) A transesterification reaction was carried out in the same manner as in Example 20 above, except that the separation membrane 2 was not used.

[0112] After 12 hours of reaction, the solution contained 0.08 mol of methyl hexanoate, 0.08 mol of 1-hexanol, 0.09 mol of hexyl hexanoate, and 0.06 mol of methanol, giving a yield of 53%.

[0113] (Comparative Example 20) A transesterification reaction was carried out in the same manner as in Example 21 above, except that the separation membrane 2 was not used.

[0114] After 12 hours of reaction, the solution contained 0.07 mol of methyl hexanoate, 0.07 mol of 1-hexanol, 0.10 mol of hexyl hexanoate, and 0.08 mol of methanol, giving a yield of 57%.

[0115] Table 2 shows the effect of reaction temperature on the transesterification reaction using methyl hexanoate and 1-hexanol as reaction substrates.

[0116] [Table 2]

[0117] When FAU zeolite membrane B was used to continuously remove by-product methanol from the reaction system, the yields of hexyl hexanoate at reaction temperatures of 60°C, 80°C, and 100°C were 63%, 80%, and 82%, respectively (Examples 20, 18, and 21). On the other hand, when the FAU zeolite membrane was not used, the yields of hexyl hexanoate at reaction temperatures of 60°C, 80°C, and 100°C were 53%, 55%, and 57%, respectively (Comparative Examples 19, 17, and 20). At all reaction temperatures, the yield was higher when a separation membrane was used. This indicates that if by-product methanol can be removed using a separation membrane, the transesterification reaction can be promoted regardless of the reaction temperature.

[0118] In a transesterification reaction using methyl hexanoate and 1-hexanol as the reaction substrates, the effect of the composition of the reaction substrate on the yield was investigated at an electric furnace temperature, i.e., a reaction temperature of 100°C.

[0119] Example 22 A transesterification reaction was carried out in the same manner as in Example 21 above, except that 0.12 mol of methyl hexanoate and 0.24 mol of 1-hexanol (molar ratio of methyl hexanoate / 1-hexanol=1 / 2) were used.

[0120] After 12 hours of reaction, the solution contained 0.01 mol of methyl hexanoate, 0.09 mol of 1-hexanol, 0.12 mol of hexyl hexanoate, and 0.004 mol of methanol, giving a yield of 94%.

[0121] Example 23 A transesterification reaction was carried out in the same manner as in Example 21 above, except that 0.09 mol of methyl hexanoate and 0.27 mol of 1-hexanol (molar ratio of methyl hexanoate / 1-hexanol=1 / 3) were used.

[0122] After 8 hours of reaction, the solution contained 0.004 mol of methyl hexanoate, 0.14 mol of 1-hexanol, 0.09 mol of hexyl hexanoate, and 0.002 mol of methanol, giving a yield of 96%.

[0123] (Comparative Example 21) A transesterification reaction was carried out in the same manner as in Example 22 above, except that the separation membrane 2 was not used.

[0124] After 12 hours of reaction, the solution contained 0.03 mol of methyl hexanoate, 0.12 mol of 1-hexanol, 0.10 mol of hexyl hexanoate, and 0.05 mol of methanol, giving a yield of 77%.

[0125] (Comparative Example 22) A transesterification reaction was carried out in the same manner as in Example 23 above, except that the separation membrane 2 was not used.

[0126] After 8 hours of reaction, the solution contained 0.02 mol of methyl hexanoate, 0.18 mol of 1-hexanol, 0.08 mol of hexyl hexanoate, and 0.05 mol of methanol, giving a yield of 78%.

[0127] Table 3 shows the effect of the molar ratio of the reactants on the transesterification reaction of hexyl hexanoate and 1-hexanol at a reaction temperature of 100°C.

[0128] [Table 3]

[0129] When the by-product methanol was continuously removed from the reaction system using FAU-type zeolite membrane B, the yields of hexyl hexanoate were 82%, 94%, and 96%, respectively, when the molar ratio of the reactant substrates (methyl hexanoate / 1-hexanol) was 1 / 1, 1 / 2, and 1 / 3 (Examples 21-23). ​​On the other hand, when a separation membrane was not used, the yields were 57%, 77%, and 78%, respectively, when the reactant substrate molar ratios were 1 / 1, 1 / 2, and 1 / 3 (Comparative Examples 20-22). The use of a separation membrane resulted in higher yields at all molar ratios. This indicates that the target product can be efficiently produced by selectively separating the by-product methanol in the transesterification reaction, even when the molar ratio of the reactant substrates is changed, by manipulating the chemical equilibrium.

[0130] (Zeolite membrane study) The effect of the Si / Al ratio of FAU-type zeolite membranes on the PV performance in 90 wt% aqueous 2-propanol (IPA) solution and 10 wt% methanol / 2-propanol (MeOH / IPA) mixture was investigated.

[0131] FAU-type zeolite membrane C was prepared on the outer surface of a porous α-alumina tube using hydrothermal synthesis. A membrane synthesis solution was prepared by mixing sodium aluminate, sodium hydroxide, water glass, and ion-exchanged water. The molar composition was 5SiO2:1Al2O3:17Na2O:1000H2O. Y-type zeolite powder (Tosoh HSZ-320NAA) was rubbed onto the outer surface of the porous α-alumina tube as nuclei for crystal growth. The tube was then placed in an autoclave with the synthesis solution and heated at 90°C for 16 hours. After synthesis, the alumina tube was cooled to room temperature, removed from the autoclave, washed with ion-exchanged water until the pH of the wash water was less than 9, and dried overnight at room temperature to obtain FAU-type zeolite membrane C.

[0132] FAU zeolite membrane D was prepared in the same manner as the FAU zeolite membrane C, except that the molar composition was 25SiO2:1Al2O3:17Na2O:1000H2O.

[0133] Table 4 shows the Si / Al ratio of the FAU-type zeolite membrane and the PV test results for a 90 wt% IPA aqueous solution and a 10 wt% MeOH / IPA mixed solution.

[0134] [Table 4]

[0135] Generally, FAU zeolite can be prepared with a Si / Al ratio in the range of 1 to 3. The Si / Al ratio of the FAU zeolite membrane prepared in the present invention was 1.0 to 2.2, and the MeOH / IPA separation factor was 5.0 or higher. This indicates that the FAU zeolite membrane is a separation membrane capable of selectively removing methanol, regardless of the Si / Al ratio, and supports the idea that the FAU zeolite membrane is particularly suitable as a separation membrane capable of promoting the membrane-type reaction of the present invention. [Industrial Applicability]

[0136] The method of the present invention solves the problems of the prior art, such as high energy consumption, poor separation ability, and discontinuous operation, and enables the synthesis of target products continuously, with high selectivity and yield, in non-aqueous organic mixed liquid phase reactions such as transesterification reactions that produce methanol, an organic by-product. Therefore, it is expected to significantly improve the economic efficiency in the production of basic chemicals, cosmetics, pharmaceuticals, and their intermediates, and is therefore of great industrial utility. [Explanation of symbols]

[0137] 1...Reaction vessel 2...Separation membrane 3...Rotary pump 4...Stir bar 5...Magnetic stirrer 6...Cooler 7...Electric furnace 8...Trap tube 9...Dewar flask 10...Switching valve

Claims

1. A method for producing a product resulting from a reaction governed by chemical equilibrium using a membrane reactor, comprising: The membrane reactor is a membrane reactor that includes a separation membrane that selectively separates by-products generated by the reaction from the reaction liquid, and the by-products are selectively and continuously separated from the reaction liquid, thereby shifting the chemical equilibrium in the reaction and allowing the reaction to proceed further; a step of reacting reaction raw materials in the presence of a catalyst to produce the product and a by-product in the membrane reactor, wherein the by-product is selectively and continuously separated from the reaction liquid by a separation membrane of the membrane reactor, and the reaction governed by chemical equilibrium is a transesterification reaction; the by-product is methanol; the separation membrane is an inorganic membrane that selectively separates methanol; methyl acetate and a monohydric alcohol having 3 or less carbon atoms are used as raw materials for the transesterification reaction; and methanol is selectively separated by the separation membrane from a reaction solution containing methanol produced by the reaction, the target product, and unreacted raw materials.

2. The method according to claim 1 , wherein a cation exchange resin is used as the catalyst.

3. The method according to claim 1 or 2, wherein a zeolite membrane is used as the separation membrane.

4. 4. The method according to claim 3, wherein the separation membrane is a membrane obtained by depositing FAU-type zeolite on a porous support.

5. The production method according to any one of claims 1 to 4, wherein the membrane reactor further comprises at least one selected from the group consisting of a supply section for supplying reaction raw materials or a catalyst, a recovery section for recovering by-products separated by the separation membrane, a discharge section for discharging a reaction liquid containing the target product, and a catalyst recovery section for recovering the catalyst.

6. The production method according to claim 5, wherein the reaction governed by chemical equilibrium is a reaction that does not reach a conversion rate of 100% due to the presence of the by-product.

7. The method according to claim 5 or 6, wherein the reaction solution is a non-aqueous mixed solution.

8. supplying reaction raw materials and / or catalyst to the membrane reactor; recovering the reaction solution containing the target product; The method according to any one of claims 5 to 7, further comprising:

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