Bonding body, separation membrane module provided with the bonding body, and alcohol production method

Abstract

The present application solves the problem of providing a bonded body having high airtightness and excellent durability under high temperature and high pressure conditions, and solves the problem by a bonded body in which a composite of a zeolite and an inorganic porous support body is bonded to a dense member with an inorganic glass or an inorganic adhesive, wherein the inorganic glass or the inorganic adhesive has a coefficient of thermal expansion of 30 x 10 ‑7 / K or more and 90 x 10 ‑7 / K or less, and a softening point of 550°C or less in the case of the inorganic glass. Further, the present application solves the problem of providing a method for efficiently producing alcohol by providing a separation membrane in an alcohol synthesis reactor by a bonding method having good airtightness and durability under high temperature and high pressure and in the presence of alcohol vapor, and solves the problem by an alcohol production method in which a raw material gas containing at least hydrogen and carbon monoxide and / or carbon dioxide is reacted in the presence of a catalyst in a reactor to obtain alcohol, wherein an alcohol-selective permeation membrane bonded to a dense member is provided in the reactor in which the reaction is performed, and alcohol produced by the reaction is taken out by permeating the selective permeation membrane.

Description

Technical Field

[0001] The present invention relates to a junction, a separation membrane assembly having the junction, and a method for manufacturing an alcohol, wherein the alcohol is preferably methanol. Background Technology

[0002] Membranes capable of gas separation are typically formed on an inorganic porous support and bonded to a dense, gas-impermeable component. In this case, bonding requires a high degree of airtightness. When a membrane capable of gas separation is used experimentally to confirm its performance, rather than in a reactor for industrial gas separation, a short-term bonding process using an instant adhesive is sufficient. However, in applications where the membrane is installed in a reactor and used stably for long-term gas separation, glass is more commonly used. Glass bonding is frequently used industrially because the membrane can be easily removed by reheating when replacing the separation membrane section. Patent Document 1 discloses a method using a membrane with a coefficient of thermal expansion of 50 × 10⁻⁶. -7 / K~80×10 -7 / K is a glass-bonded metal gas separation membrane and a metal component. Furthermore, Patent Document 2 discloses a gas conduit for bonding a zeolite membrane and alumina using a separation membrane sealing composition made of a specific glass containing a specified amount of B2O3 and PbO and alumina. That is, until now, considering the coefficient of thermal expansion, metal components are generally used in the case of metal separation membranes, and dense ceramic components are used in the case of ceramic supports. Furthermore, Patent Document 3 discloses the use of a component with a coefficient of thermal expansion of 55 × 10⁻⁶. -7 / K~65×10 -7 / K glass is used to seal ceramic components and Fe-Ni-Co alloy components.

[0003] Here, when using zeolite membranes as the gas separation membrane, high-temperature processing is not preferred due to concerns about the heat resistance of the zeolite membrane. Processing at temperatures above 900°C, as disclosed in Patent Documents 1 and 3, raises concerns about structural degradation such as zeolite membrane breakage, leading to reduced separation performance. Furthermore, high-temperature bonding not only requires heating and cooling time, but also causes damage to the bonding joint itself due to temperature changes, affecting the separation performance or lifespan of the bonded assembly. In mass production of bonded assemblies, this also leads to reduced efficiency and increased costs.

[0004] On the other hand, the bond formed by joining the separation membrane needs to possess sufficient airtightness while being able to withstand operating temperature and pressure for long-term use. However, existing bonds do not meet this requirement. For example, the strength and durability of a bond formed by joining a separation membrane with a ceramic such as alumina disclosed in Patent Document 2 are insufficient. Especially under long-term use at high temperature and pressure, coupled with factors such as vibration caused by contact with fluid, cracks may occur, leading to further damage. Furthermore, the use of lead glass as a bonding material has been proposed, which possesses sufficient airtightness while being resistant to temperature changes and reaction pressures, allowing for long-term use. For example, as disclosed in Patent Document 2, by using glass with PbO as the main component, the firing temperature can be kept below 600°C. However, it is known that lead accumulation in the body can cause chronic poisoning, and its use poses environmental problems, contradicting the trend of restricting lead use in various countries around the world. Furthermore, as disclosed in Patent Document 4, when a swelling resin such as epoxy resin is used as a binder, if it is exposed to an organic solvent under high temperature and high pressure conditions, as shown in the comparative examples below, deterioration may occur, leading to breakage of the bond.

[0005] Methods for producing methanol from gases containing hydrogen and carbon monoxide (hereinafter, synthesis gases) have long been known, for example, methods using copper-based catalysts (copper-zinc catalysts, copper-chromium catalysts). The reaction to produce methanol from syngas is an equilibrium reaction, which is more favorable at lower temperatures and higher pressures. Since the reaction rate decreases at lower temperatures, the typical methanol production process is carried out under harsh conditions such as 200–300°C and 5–10 MPaG (or higher pressures). Therefore, it consumes a great deal of energy and imposes many restrictions on equipment when producing methanol.

[0006] As a method for efficiently producing methanol, various methods have been proposed to remove methanol from the reaction system, thereby shifting the gas composition in the reactor away from the equilibrium composition and carrying out the reaction at a conversion rate exceeding the equilibrium conversion rate.

[0007] In addition, patent documents 5, 6, 7 and 8 propose a method of setting a separation membrane in a methanol synthesis reactor and using the separation membrane to remove methanol or water from the reaction system, thereby increasing the conversion rate to above the equilibrium conversion rate.

[0008] Furthermore, Non-Patent Literature 1 reports a method for installing a separation membrane sealed with graphite packing in a high-temperature and high-pressure methanol reactor. Non-patent literature 2 and 3 report the temperature and pressure dependence of the reaction rates of methanol synthesis without the use of a separation membrane and the concurrent water-gas shift reaction. Existing technical documents Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 7-163827 Patent Document 2: Japanese Patent Application Publication No. 10-180060 Patent Document 3: Japanese Patent Application Publication No. 2013-203602 Patent Document 4: Japanese Patent Application Publication No. 2007-50322 Patent Document 5: Japanese Patent Publication No. 9-511509 Patent Document 6: Japanese Patent Application Publication No. 2016-117726 Patent Document 7: Japanese Patent Application Publication No. 2016-174996 Patent Document 8: Japanese Patent Application Publication No. 2007-55970 Non-patent literature

[0010] Non-patent literature 1: Chem. Eng. Process. 43 (2004), 1029 Non-patent literature 2: Szarawara, J. Reychman, K. 1980. Inz Chem Proc., 1:331 Non-patent literature 3: Vanden Bussche KM, Froment GF, 1996. J. Catal., 161, 1-10 Summary of the Invention The problem that the invention aims to solve

[0011] The object of the present invention is to provide a composite body formed by joining a zeolite with an inorganic porous support and a dense component, which achieves high airtightness while considering the environmental impact of suppressing lead use, and particularly excellent durability under high temperature and high pressure conditions (the first problem to be solved).

[0012] The objective is also to achieve high airtightness, substantially avoid zeolite damage during bonding, and especially to provide excellent durability under high temperature and high pressure conditions when providing a composite body formed by bonding zeolite with an inorganic porous support and a dense component (the second problem to be solved).

[0013] The objective is also to achieve high airtightness, particularly excellent durability under high temperature and high pressure conditions and / or in the presence of solvents or gases, especially organic solvents or organic gases, when providing a composite body formed by joining zeolite with an inorganic porous support and a dense component, by a simple method that does not require high temperature calcination, etc. (the third problem to be solved).

[0014] In the methods for setting up a separation membrane in a methanol synthesis reactor as proposed in Patent Documents 5, 6, 7, and 8, it is necessary to maintain a long-term sealed gas supply side (high pressure) and gas permeation side (low pressure) in the presence of methanol vapor under high temperature and high pressure. The method of connecting the separation membrane with other components becomes a problem to be solved. However, Patent Documents 5, 6, and 7 do not describe a specific connection method, nor do they describe embodiments under high temperature and high pressure conditions. Although Patent Document 8 describes an example of removing water from a methanol synthesis reactor using a separation membrane under high temperature and high pressure conditions such as 200°C and 3 MPaG, it similarly does not describe a specific bonding method, nor does it clarify the sealing performance or durability.

[0015] The mechanical sealing method using graphite gaskets, etc., described in Non-Patent Literature 1 is not suitable for industrial use because it requires laborious tightening of the membrane one by one and the volume of the joint increases due to the need to store the graphite gaskets. In addition, the additives used to form the graphite into gaskets do not have durability against methanol vapor and cannot be used for a long time.

[0016] The present invention was made based on the above circumstances, and its purpose is to provide a method for efficiently producing methanol by setting a separation membrane in a methanol synthesis reactor through a bonding method with good sealing and durability under high temperature and high pressure and in the presence of methanol vapor (the fourth problem to be solved).

[0017] This invention significantly improves the yield by using zeolite or similar materials as a separation membrane to remove the generated alcohols from the reactor, as described above. However, since the reaction to obtain alcohols is a vigorous exothermic reaction, the heat of exothermic reaction increases with the amount of alcohol produced, resulting in an increase in the temperature inside the reactor. This can damage the zeolite and reduce the efficiency of alcohol separation. Furthermore, increasing the feed flow rate raises the temperature inside the reactor, and the equilibrium reaction shifts towards the hydrogen and carbon monoxide and / or carbon dioxide feedstocks due to the increased temperature. This is also a problem that needs to be addressed in order to obtain alcohols more efficiently.

[0018] Furthermore, when the generated alcohols are not removed from the reactor and the catalytic reaction is carried out alone, the temperature inside the reactor rises due to the heat of reaction, shifting the equilibrium towards the feed side and inhibiting the alcohol formation reaction. Therefore, the temperature rise inside the reactor becomes slow, resulting in an upper limit to the reactor temperature due to equilibrium constraints. On the other hand, in the case of combined catalytic reaction and separation membrane, the product is extracted outside the system, thus reducing the equilibrium constraint and creating a new problem that needs to be addressed: the reaction temperature can easily rise significantly. Therefore, the inventors also aim to provide a manufacturing apparatus and method that, by removing the heat of reaction generated from the reactor and using that heat, for example, to heat hydrogen as a raw material, as well as carbon monoxide and / or carbon dioxide, can not only increase the yield but also reduce the energy required for alcohol production (the fifth problem to be solved). Technical solutions to the problem

[0019] The inventors conducted in-depth research and discovered that in order to properly bond the composite of zeolite and inorganic porous support with dense components, the above-mentioned problems can be solved by using inorganic glass or inorganic adhesive with specific coefficients of thermal expansion and softening points, thus completing the invention. Furthermore, the inventors discovered that when producing methanol from a feed gas containing hydrogen and carbon monoxide and / or carbon dioxide, the above-mentioned problems can be solved by setting a methanol selectively permeable membrane in the reactor, which is bonded to a dense component using a specific bonding material, thus completing the invention.

[0020] The first embodiment of the present invention includes the following methods: [A1-1] A joint is formed by bonding a composite of zeolite and an inorganic porous support and a dense component through lead-free inorganic glass, wherein the coefficient of thermal expansion of the lead-free inorganic glass is 30 × 10⁻⁶. -7 / K or higher and 90×10 -7 It has a temperature below / K and a softening point below 550℃. [A1-2] According to the joint described in [A1-1], the joint portion of the composite and the dense component is covered by a sealing membrane. [A1-3] According to the bonding body described in [A1-2], the sealing film is a silicon dioxide film. [A1-4] According to any one of [A1-1] to [A1-3], the lead-free inorganic glass contains SnO and / or B2O3. [A1-5] The coefficient of thermal expansion of the dense component of the joint according to any one of [A1-1] to [A1-4] is 30 × 10⁻⁶. -7 / K or higher and 200×10 -7 / K or below. [A1-6] A method of using a joint, wherein the joint described in any one of [A1-1] to [A1-5] is used under high temperature conditions of 100°C to 500°C and / or high pressure conditions of 0.5 to 10 MPa. [A1-7] A separation membrane assembly having the junction as described in any one of [A1-1] to [A1-6]. [A1-8] A reactor having the separation membrane assembly described in [A1-7]. [A1-9] A bonding method for joining a composite of zeolite and an inorganic porous support and a dense component using lead-free inorganic glass, wherein the coefficient of thermal expansion of the lead-free inorganic glass is 30 × 10⁻⁶. -7 / K or higher and 90×10 -7 It has a temperature below / K and a softening point below 550℃.

[0021] The second embodiment of the present invention includes the following methods: [A2-1] A joint is formed by bonding a composite of zeolite and an inorganic porous support and a dense component through an inorganic glass, wherein the dense component is a metal component and the coefficient of thermal expansion of the inorganic glass is 30 × 10⁻⁶. -7 / K or higher and 90×10 -7 It has a temperature below / K and a softening point below 550℃. [A2-2] According to the joint described in [A2-1], the joint portion of the composite and the dense component is covered by a sealing membrane. [A2-3] According to the bonding body described in [A2-2], the sealing film is a silicon dioxide film. [A2-4] According to any one of [A2-1] to [A2-3], the inorganic glass contains SnO and / or B2O3. [A2-5] According to any one of [A2-1] to [A2-4], the coefficient of thermal expansion of the dense component is 30 × 10⁻⁶. -7 / K or higher and 200×10 -7 / K or below. [A2-6] A method of using a joint, wherein the joint described in any one of [A2-1] to [A2-5] is used under high temperature conditions of 100°C to 500°C and / or high pressure conditions of 0.5 to 10 MPa. [A2-7] A separation membrane assembly having the junction as described in any one of [A2-1] to [A2-5]. [A2-8] A reactor having the separation membrane assembly described in [A2-7]. [A2-9] A bonding method is used to bond a composite of zeolite and an inorganic porous support and a dense component using inorganic glass, wherein the dense component is a metal component and the coefficient of thermal expansion of the inorganic glass is 30 × 10⁻⁶. -7 / K or higher and 90×10 -7 It has a temperature below / K and a softening point below 550℃.

[0022] The third embodiment of the present invention includes the following methods: [B1] A bonding body, which is formed by bonding a composite of zeolite and an inorganic porous support and a dense component with an inorganic adhesive, wherein the coefficient of thermal expansion of the inorganic adhesive after curing is 30 × 10⁻⁶. -7 / K~90×10 -7 / K. [B2] A bonding body, which is formed by bonding a composite of zeolite and an inorganic porous support and a dense component with an inorganic adhesive, wherein the difference in the coefficient of thermal expansion between the dense component and the cured inorganic adhesive is 50 × 10⁻⁶. -7 / K. [B3] According to the joint described in [B1] or [B2], the inorganic adhesive contains a metal alkoxide. [B4] The joint body according to any one of [B1] to [B3], wherein the joint portion of the composite body and the dense component is covered by a sealing membrane. [B5] According to the bonding body described in [B4], the sealing film is a silicon dioxide film. [B6] The joint according to any one of [B1] to [B5], wherein the coefficient of thermal expansion of the dense component is 30 × 10⁻⁶. -7 / K~200×10 -7 / K. [B7] A method of using a joint, wherein the joint described in any one of [B1] to [B6] is used under high temperature conditions of 100°C to 500°C and / or high pressure conditions of 0.5 to 10 MPa. [B8] A separation membrane assembly having the junction as described in any one of [B1] to [B6]. [B9] A reactor having the separation membrane assembly described in [B8]. [B10] A bonding method comprising bonding a composite of zeolite and an inorganic porous support and a dense component using an inorganic adhesive, wherein the coefficient of thermal expansion of the cured inorganic adhesive is 30 × 10⁻⁶. -7 / K~90×10 -7 / K.

[0023] The fourth embodiment of the present invention includes the following methods: [C1-1] A method for producing methanol, comprising reacting a feed gas in a reactor in the presence of a catalyst to obtain methanol, wherein the feed gas comprises at least: hydrogen, and carbon monoxide and / or carbon dioxide. In the reactor where the reaction takes place, a methanol-selective permeable membrane is provided, which is bonded to a dense component by a bonding material. The methanol generated during the reaction passes through the selective permeable membrane and is then removed. The bonding material is mainly composed of inorganic oxides and has a linear expansion coefficient of 30 × 10⁻⁶. -7 / K or higher and 90×10 -7 / K or below. [C1-2] In the methanol manufacturing method described in [C1-1], the methanol selective permeation membrane is a zeolite membrane. [C1-3] In the methanol manufacturing method according to [C1-1] or [C1-2], the dense component is metal. [C1-4] In the methanol manufacturing method according to any one of [C1-1] to [C1-3], the methanol partial pressure on the gas supply side of the methanol selective permeation membrane in the reactor is 0.1 MPa or more and 6 MPa or less. [C1-5] In the methanol manufacturing method according to any one of [C1-1] to [C1-4], the temperature inside the reactor is above 200°C and below 300°C. [C1-6] In the methanol manufacturing method according to any one of [C1-1] to [C1-5], the pressure on the gas supply side of the methanol selectively permeable membrane in the reactor is 1 MPaG or more and 8 MPaG or less. [C1-7] In the methanol manufacturing method according to any one of [C1-1] to [C1-6], the linear expansion coefficient of the dense component is 30 × 10⁻⁶. -7 / K or higher and 200×10 -7 / K or below. [C1-8] In the methanol manufacturing method according to any one of [C1-1] to [C1-7], the dense component is Kovar alloy. [C1-9] In the methanol manufacturing method according to any one of [C1-1] to [C1-8], the inorganic oxide is an inorganic glass or an inorganic binder. [C1-10] A methanol manufacturing apparatus, used in a method for producing methanol by reacting a feed gas in a reactor in the presence of a catalyst, wherein the feed gas comprises at least: hydrogen, and carbon monoxide and / or carbon dioxide, wherein the methanol manufacturing apparatus has the following structure: in the reactor where the reaction takes place, a methanol selectively permeable membrane is provided, which is bonded to a dense component by a bonding material, allowing the methanol generated in the reaction to pass through the selectively permeable membrane and be removed, wherein the bonding material is mainly composed of inorganic oxides and has a linear expansion coefficient of 30 × 10⁻⁶. -7 / K or higher and 90×10 -7 / K or below.

[0024] The fourth embodiment of the present invention also includes the following: [C2-1] A method for producing methanol, comprising reacting a feed gas in a reactor in the presence of a catalyst to obtain methanol, wherein the feed gas comprises at least: hydrogen, and carbon monoxide and / or carbon dioxide. The reactor in which the reaction takes place is equipped with a methanol selective permeation membrane, which allows the methanol produced in the reaction to pass through the selective permeation membrane and be removed. [C2-2] According to the methanol manufacturing method described in [C2-1], the catalyst is present adjacent to the methanol selectively permeable membrane. [C2-3] A methanol manufacturing apparatus, used in a method of producing methanol by reacting a feed gas in a reactor in the presence of a catalyst, wherein the feed gas contains at least: hydrogen, and carbon monoxide and / or carbon dioxide, wherein the methanol manufacturing apparatus has the following structure: a methanol selectively permeable membrane is provided in the reactor in which the reaction is carried out, so that the methanol generated by the reaction is removed through the selectively permeable membrane. [C2-4] In the methanol manufacturing apparatus according to [C2-3], the catalyst is present adjacent to the methanol selectively permeable membrane. The fifth embodiment of the present invention includes the following methods: [D1] An alcohol manufacturing apparatus for synthesizing alcohols by reacting raw materials in the presence of a catalyst, said raw materials comprising at least: hydrogen, and carbon monoxide and / or carbon dioxide. The manufacturing apparatus includes: a reactor having an alcohol selectively permeable membrane with zeolite, a heat recovery device for recovering at least a portion of the heat of reaction from the reactor, and a heat supply device for supplying the heat recovered by the heat recovery device. [D2] According to the alcohol manufacturing apparatus described in (D1), the heat recovery device is a heat exchanger installed inside or adjacent to the reactor. [D3] In the alcohol manufacturing apparatus according to (D1) or (D2), the heat supply device is a heat exchanger. [D4] In any one of the alcohol manufacturing apparatuses according to (D1) to (D3), the methanol / hydrogen permeation coefficient ratio of the alcohol selectively permeable membrane is 10 or more. [D5] An alcohol manufacturing method comprising a synthesis step of reacting raw materials to synthesize an alcohol in the presence of a catalyst, wherein the raw materials comprise at least: hydrogen, and carbon monoxide and / or carbon dioxide, the alcohol manufacturing method comprising: a separation and recovery step of separating and recovering the obtained alcohol in a reactor using an alcohol-selective permeation membrane having zeolite; and a heat recovery step of recovering at least a portion of the heat of reaction generated in the synthesis step from the reactor; and wherein the separation and recovery step is performed simultaneously with the heat recovery step. [D6] According to the alcohol manufacturing method described in (D5), in the synthesis step, the temperature inside the reactor is controlled to be above 200°C and below 300°C. [D7] The alcohol manufacturing method according to (D5) or (D6) includes: a supply step, which supplies at least a portion of the heat of reaction recovered in the heat recovery step for heating one or more raw materials selected from hydrogen, carbon monoxide and carbon dioxide before they are introduced into the reactor. [D8] In the alcohol production method according to any one of (D5) to (D7), the ratio of the area of ​​the alcohol-selectively permeable membrane to the volume of the catalyst is 5m². 2 / m 3 The above 150m 2 / m 3 the following. Invention Effects

[0025] According to a first embodiment of the present invention, when a composite of zeolite serving as a separation membrane and an inorganic porous support and a dense component are manufactured as a joint, an article can be provided that achieves high airtightness while taking into account the environment by using lead-free inorganic glass for bonding, and has excellent durability, especially under high temperature and high pressure conditions.

[0026] Furthermore, according to the second embodiment of the present invention, when the composite of the zeolite serving as a separation membrane and the inorganic porous support and the dense component are manufactured into a joint, by making the dense component a metal component and using a specific inorganic glass as a glass-based adhesive, a joint with reduced damage to the zeolite during bonding, high airtightness, and sufficient durability under high temperature and high pressure conditions can be provided.

[0027] Furthermore, according to the third embodiment of the present invention, when the zeolite-inorganic porous support composite and dense component serving as a separation membrane are manufactured into a joint, a simple method without high-temperature calcination can be used to provide a zeolite-inorganic porous support composite and dense component with high airtightness, which can be used for a long time under high temperature and high pressure conditions and / or in the presence of solvents or gases, especially organic solvents or organic gases, as well as a separation membrane assembly having the joint.

[0028] Furthermore, according to a fourth embodiment of the present invention, in the production of methanol, a method for efficiently producing methanol can be provided by providing a separation membrane in a methanol synthesis reactor through a bonding method that has good sealing and durability under high temperature and high pressure and in the presence of methanol vapor, thereby allowing the methanol generated in the reaction to be removed through a selectively permeable membrane.

[0029] Furthermore, according to the fifth embodiment of the present invention, since the temperature inside the reactor does not rise excessively, damage to the zeolite is reduced, and the separation capability of the zeolite membrane can be maintained for a long time. In addition, since the alcohol production decreases at high temperatures in this equilibrium reaction, the temperature inside the reactor does not rise excessively, and the yield can be maintained. Furthermore, it is necessary to heat the hydrogen, carbon monoxide, and / or carbon dioxide used as feedstocks to a certain extent before supplying them to the catalyst. By preferably supplying the recovered heat to the feedstocks, an alcohol production apparatus and method that can improve the overall energy efficiency of the system can be provided. Attached Figure Description

[0030] Figure 1 This is a cross-sectional schematic diagram of a composite material formed by bonding zeolite with an inorganic porous support and dense components using inorganic glass or inorganic adhesive. Figure 2 This is a cross-sectional schematic diagram of a composite material formed by bonding zeolite with an inorganic porous support and dense components using inorganic glass or inorganic adhesive. Figure 3 This is a cross-sectional schematic diagram of a composite material formed by bonding zeolite with an inorganic porous support and dense components using inorganic glass or inorganic adhesive. Figure 4 This is a cross-sectional schematic diagram showing one embodiment of the reactor. Figure 5 This is a cross-sectional schematic diagram illustrating one embodiment of joining a zeolite membrane to a piping flange via a bonding material. Figure 6 This is a cross-sectional schematic diagram illustrating one embodiment of joining a zeolite membrane to a piping via a bonding material. Figure 7 This is a cross-sectional schematic diagram illustrating one embodiment of bonding a zeolite membrane to a reactor via a bonding material. Figure 8This is a flowchart illustrating a summary of the manufacturing process involved in one embodiment of the present invention. Figure 9 This is a cross-sectional schematic diagram showing one embodiment of a reactor with a heat exchanger. Figure 10 This is a flowchart illustrating a summary of the manufacturing process involved in one embodiment of the present invention. Figure 11 This is a flowchart illustrating an outline of the manufacturing process involved in the comparative example implementation. Figure 12 This is a flowchart illustrating an outline of the manufacturing process involved in the comparative example implementation. Figure 13 This is a flowchart illustrating a summary of the manufacturing process involved in one embodiment of the present invention. Explanation of reference numerals in the attached figures 1: A composite of zeolite and inorganic porous support 2: Cap 3: Dense components (piping) 4: Bonding materials 10: Reactor 11: A flange composed of dense components 13: Catalyst 101: Heat Exchanger Detailed Implementation

[0031] The present invention will be described in detail below, but the description of the constituent elements described below is only one example (representative example) of the implementation of the present invention. The present invention is not limited to these contents and can be implemented in various modifications within the scope of its spirit.

[0032] <<First Implementation Method>> The first embodiment of the present invention is a joint body, which is a joint body formed by bonding a composite of zeolite and an inorganic porous support and a dense component through lead-free inorganic glass, wherein the coefficient of thermal expansion of the lead-free inorganic glass is 30 × 10⁻⁶. -7 / K or higher and 90×10 -7 It has a temperature below / K and a softening point below 550℃.

[0033] Lead-free inorganic glass In this embodiment, lead-free inorganic glass refers to inorganic glass with a lead (Pb) content converted to PbO of 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, particularly preferably 1% by mass or less, and most preferably 0% by mass.

[0034] The coefficient of thermal expansion of the lead-free inorganic glass involved in this embodiment is typically 30 × 10⁻⁶. -7 / K or higher, preferably 40×10 -7 / K or higher, preferably 45×10 -7 / K or higher, in addition, it is usually 90×10 -7 / K or less, preferably 80×10 -7 / K or less, preferably 75×10 -7 / K or below.

[0035] In this embodiment, the coefficient of thermal expansion of the lead-free inorganic glass is typically 60% or more, preferably 70% or more, and more preferably 80% or more, and is generally 200% or less, preferably 150% or less, and more preferably 120% or less. By making the coefficient of thermal expansion of the lead-free inorganic glass below the aforementioned upper limit, when the temperature decreases after bonding at the melting temperature of the lead-free inorganic glass, tensile stress is less likely to be generated inside the joint, and cracks in the joint are suppressed. On the other hand, by making the coefficient of thermal expansion of the glass above the aforementioned lower limit, gaps are less likely to be generated between the composite and the dense component within the operating temperature range of the joint, and leakage of the target gas from these gaps to the refined gas side can be suppressed. Preferably, in the test method described in the Examples section of this specification, the air permeability of the joint obtained in this way is preferably 10 sccm or less, more preferably 8 sccm or less, and most preferably 5 sccm or less. Furthermore, even after adding 1 / 16 methanol and 1 / 16 demineralized water by volume in the autoclave, heating to 280°C for 1 hour, maintaining this state for 48 hours, allowing natural cooling, and drying at 120°C under normal pressure for 4 hours, the air permeability of the bonded joint is measured again. The air permeability is 10 sccm or less, more preferably 8 sccm or less, and most preferably 5 sccm or less. Since conditions such as the thermal expansion coefficient are met, even with longer-term methanol production, no problems will occur at the joint, making this method even more preferable.

[0036] When a separation assembly having the joint described in this embodiment is used in industry, it will repeatedly cycle between room temperature and operating temperature, and will also operate for extended periods at the operating temperature. Therefore, it is required that the joint formed by the lead-free inorganic glass will not leak the gas to be separated, even under these high temperature and high pressure conditions. By setting the coefficient of thermal expansion of the lead-free inorganic glass as described above, leakage of the gas to be separated can be suppressed.

[0037] The lead-free inorganic glass involved in this embodiment has a softening point of 550°C or less, preferably 530°C or less, and more preferably 480°C or less. Typically, the glass frit of the lead-free inorganic glass is made to flow by calcining it at a temperature approximately 50°C above its softening point. Therefore, by keeping the softening point of the lead-free inorganic glass within the above-mentioned range, zeolite can be chemically bonded to the lead-free inorganic glass at a relatively low temperature of around 600°C or less, and the lead-free inorganic glass can enter the pores of the composite, allowing the composite to be mechanically and firmly bonded to the dense component. Furthermore, because the bonding temperature is relatively low, damage to the zeolite due to heating during bonding is reduced.

[0038] As for the lead-free inorganic glass, there are no particular limitations as long as it has the aforementioned coefficient of thermal expansion and softening point. Examples of components contained in lead-free inorganic glass include SiO2, Al2O3, ZnO, P2O5, Bi2O3, BaO, TiO2, TeO2, V2O5, B2O3, and SnO. Among these, from the perspective of improving sealing performance, lead-free inorganic glass particularly preferably contains B2O3 and / or SnO. Specific examples of lead-free inorganic glasses containing B2O3 and / or SnO include SnO-P2O5 series glasses, Bi2O3-ZnO series glasses, Bi2O3-B2O3 series glasses, Bi2O3-B2O3-SiO2 series glasses, and Bi2O3-ZnO-B2O3 series glasses. Commercially available glass materials for lead-free inorganic glass include “FP-74”, “KP312E”, “FP-67”, “BNL115BB”, “ASF-1094”, “ASF-1098”, “ASF-1109” (all manufactured by AGC Corporation); “BF-0606”, “BF-0901” (all manufactured by Nippon Electric Glass Corporation); etc.

[0039] When lead-free inorganic glass contains SnO, there is no particular limitation on its content, which is usually less than 80% by mass, preferably less than 75% by mass, more preferably less than 70% by mass, and usually less than 10% by mass, preferably more than 20% by mass, more preferably more than 30% by mass. By ensuring the SnO content falls within this range, the fluidity of the glass can be adequately guaranteed, making it easy to achieve sufficient sealing performance. The specific effects of adding SnO are not yet clear, but it is known that SnO can act as a reducing agent, suggesting that it may modify the oxide film on the surface of dense components or inhibit the increase in oxide film thickness during bonding processes, thereby improving sealing performance.

[0040] On the other hand, when lead-free inorganic glass contains B2O3, its content is typically 25% by mass or less, preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 15% by mass or less. Furthermore, it is typically 1% by mass or less, preferably 2% by mass or more, and more preferably 3% by mass or more. Adding B2O3 improves its wettability with dense components, making it easier to improve sealing. On the other hand, a higher B2O3 content tends to increase the softening point, reducing the flexibility in mixing other components to achieve a softening point below 550°C. Therefore, it is preferable to select components within the aforementioned range. Furthermore, since B2O3 is soluble in water and alcohol, and there is a possibility of exposure to these substances under high temperature or high pressure conditions, it is preferable to select components below the aforementioned upper limit.

[0041] In addition, methods for quantifying the content of SnO and B2O3 include XRF (fluorescence X-ray analysis) and ICP (inductively coupled plasma atomic emission spectrometry).

[0042] There are no particular restrictions on the form of lead-free inorganic glass. Powdered glass frit, tablets formed by pressing glass frit, tablets used as sintered products, and glass slurries formed by uniformly dispersing glass frit in organic solvents or binders are all acceptable. In mass production of bonded components, tablet or slurry forms are particularly preferred due to their ability to improve production efficiency.

[0043] Zeolite The main zeolite constituting the zeolite film preferably contains a zeolite with a small-pore structure having oxygen rings of 12 or fewer or more than 6 members, and more preferably contains a zeolite with a small-pore structure having oxygen rings of 10 or fewer or more than 6 members. The 'n' value in the context of zeolites with n-membered oxygen rings refers to the pores containing the largest number of oxygen atoms, formed by oxygen and T elements (elements other than oxygen in the framework) that constitute the zeolite framework. For example, MOR-type zeolites, in the presence of pores with 12-membered and 8-membered oxygen rings, are considered zeolites with 12-membered oxygen rings.

[0044] Examples of zeolites with a small-pore structure containing oxygen rings of twelve or fewer members or more members include those coded by the International Zeolite Association (IZA): AEI, AEL, AFI, AFG, ANA, ATO, BEA, BRE, CAS, CDO, CHA, CON, DDR, DOH, EAB, EPI, ERI, ESV, EUO, FAR, FAU, FER, FRA, HEU, GIS, GIU, GME, GOO, ITE, KFI, LEV, LIO, LOS, LTA, LTL, LTN, MAR, MEP, MER, MEL, MFI, MON, MOR, MSO, MTF, MTN, MTW, MWW, NON, NES, OFF, PAU, PHI, RHO, RTE, RTH, RUT, SGT, SOD, STI, STT, TOL, TON, TSC, UFI, VNI, WEI, YUG, etc. Preferably, one of these is selected arbitrarily. Furthermore, more preferably, the conjugate of the present invention is not intended to allow molecules to pass through a simple molecular sieve, i.e., a sieve based solely on molecular size differences, but rather the zeolite is used for the purpose of selectively adsorbing the target substances, for example, to allow large molecules to pass through or to separate molecules of similar size from each other. That is, more preferably, the target substances are separated by selective adsorption on the surface of the zeolite. The selective adsorption capacity of such zeolites weakens when the operating temperature is too high. The effects of the present invention are more pronounced, for example, at temperatures below 500°C.

[0045] <Inorganic Porous Support> Because zeolites lack plasticity, they are fabricated as supports on certain substrates during film formation. The supports are porous, allowing gas molecules to penetrate them; for example, they have a large number of tiny, continuous, three-dimensional pores.

[0046] In this embodiment, the material constituting the support is preferably a chemically stable material that does not react with the gas being treated and has excellent mechanical strength. Specifically, various oxide ceramics such as alumina, silicon dioxide, silicon dioxide-alumina, mullite, cordierite, and zirconium oxide can be used, as well as silicon carbide, carbon, glass, etc. Furthermore, the shape of the support varies depending on the application of the zeolite membrane. In particular, zeolite membranes on cylindrical supports are suitable for batch processes, circulation processes (including recycling processes) due to their high strength in withstanding external pressure.

[0047] In this embodiment, for example, a cylindrical support is prepared, and zeolite microcrystals are first loaded into small holes. Loading methods include impregnation, friction, suction, and immersion. These microcrystals act as nuclei during the growth of the crystals constituting the zeolite film, and are also called seed crystals. In the zeolite growth process, hydrothermal synthesis can be used in the same manner as in zeolite synthesis. The thickness of the zeolite film in the zeolite film composite is not particularly limited, but is typically 0.1 μm or more, preferably 0.5 μm or more, or typically 50 μm or less, preferably 20 μm or less. By maintaining an appropriate film thickness, density can be ensured, and high selectivity of the film can be maintained. Furthermore, sufficient permeation of the gas to be extracted can be achieved without unnecessarily increasing the pressure. Furthermore, when the matrix is ​​tubular, the surface covered by the zeolite can be the outer side of the tube, the inner side of the tube, or both. In the process of growing zeolite crystals on a support, the process can be carried out in batches with both ends of the support open.

[0048] <Dense Components> A dense component is a component that possesses a degree of tightness (fineness) to the extent that the gas supplied to the reaction or the gas produced after the reaction does not leak out of the component. There are no particular limitations on components possessing such tightness, and metals are typically used. Examples of metals mentioned here include stainless steel pipes made of stainless steel, ceramics such as alumina and zirconium oxide, and alloys such as Kovar. The coefficient of thermal expansion of dense components is typically 30 × 10⁻⁶. -7 / K or higher and 200×10 -7 For values ​​below / K, the lower limit is preferably 35×10. -7 / K or higher, preferably 40×10 -7 / K or higher, further preferably 45×10 -7 / K or higher. The upper limit is preferably 150×10 -7 / K or less, more preferably 120×10 -7 Below / K, 85×10 is further preferred. -7 / K or below. By making the coefficient of thermal expansion of the dense component within the above range, the difference between its coefficient of thermal expansion and that of lead-free inorganic glass is small, thus ensuring good sealing and durability. Furthermore, the coefficient of thermal expansion in this invention refers to the coefficient of linear expansion, which represents the proportion of change in the length of a solid as temperature increases. It is performed according to the methods described in JIS Z 2285 (metallic materials), JIS R 1618 (ceramics), etc. The coefficient of thermal expansion can be measured within a range where the length of thermal expansion changes linearly with temperature; in this specification, the coefficient of thermal expansion is typically a value measured at 30–250°C.

[0049] In this embodiment, the connection can also be made at both ends when the composite is a cylindrical support. For example, in a mixed gas separation process using a cylindrical zeolite membrane composite, separation is achieved by filling the outside of the cylindrical support with the zeolite membrane with mixed gas and applying pressure, or by vacuum degassing the inside. Therefore, one end can be sealed with a cap and a pipe connected to the other end, or pipes can be connected to both ends.

[0050] The method of joining a composite with a zeolite film on its surface to a cap made of dense components or to a pipe made of dense components with end structures similar to caps can be any method if it is a method that can join the composite and the cap with lead-free inorganic glass. For example, the following method can be used: filling the recess of the dense component with lead-free inorganic glass, placing the composite with a zeolite film on its surface on it, and then firing it under a load with a weight placed on top of the composite to join them.

[0051] Regarding the firing temperature for bonding the composite to the dense component using lead-free inorganic glass, it must be above the softening point of the lead-free inorganic glass used. Therefore, the firing temperature is typically above the softening point +10°C, preferably above the softening point +30°C, and more preferably above the softening point +50°C. Furthermore, to avoid thermal damage to the zeolite film, it is typically below 600°C, preferably below 580°C, and more preferably below 560°C. Additionally, the firing time after reaching the firing temperature is typically 5 to 90 minutes, preferably 10 minutes or more, more preferably 20 minutes or more, and preferably below 60 minutes, and more preferably below 40 minutes. The following text uses Figures 1-3 This illustrates an example of a composite material formed by bonding zeolite with an inorganic porous support and a dense component using lead-free inorganic glass. like Figure 1 As shown, the zeolite and the inorganic porous support composite 1 and flange 11 can also be directly joined by lead-free inorganic glass 4. In this embodiment, the risks of gas leakage and other problems associated with the deterioration of the connection between components over time can be reduced. In this case, flange 11 becomes a dense component. On the other hand, it can also be like Figure 2 As shown, the zeolite and the inorganic porous support composite 1 and the piping 3 are joined only by lead-free inorganic glass 4. Since the lead-free inorganic glass of this embodiment has high airtightness and durability, such a joint is possible. In this case, the piping 3 becomes a dense component. Figure 3This is a cross-sectional schematic diagram illustrating an example of a zeolite-inorganic porous support composite 1 and a piping 3 joined together by lead-free inorganic glass 4. The zeolite-inorganic porous support composite 1 is joined to the piping 3 by lead-free inorganic glass 4. The piping 3 is joined in such a way that it covers the zeolite-inorganic porous support composite 1. Furthermore, the "joint body" of the present invention refers to a composite of zeolite and inorganic porous support and a dense component joined together, which is a component that can be removed when the performance of the composite deteriorates and it is replaced. However, when there is no such removal mechanism, for example when it is installed in a reactor such as a methanol synthesis reactor, it includes a dense component that exists inside the reactor.

[0052] <Sealing film> In this embodiment, it is preferable that the joint between the composite and the dense component is covered by a sealing film. The joint may have micropores such as cracks and pinholes on its surface due to the calcination process of the lead-free inorganic glass used for bonding. Therefore, to improve sealing performance, it is preferable to perform a sealing treatment on the joint to block these micropores. Furthermore, covering the joint with a sealing film is also ideal because the sealing film formed by the sealing treatment can suppress deterioration and damage such as pinholes in the joint.

[0053] Examples of sealing agents that can form a sealing film include inorganic materials such as silica and various types of alumina; and organic polymers such as silicone resins, epoxy resins, and fluorinated resins. These agents may contain solvents or be solvent-free. In this embodiment, inorganic sealing agents, particularly silica, are preferred for their adhesion to lead-free inorganic glass and their gas barrier properties. Furthermore, silicone resins may also be suitable for forming a dense film. The amount of sealing agent applied can be appropriately determined based on the desired film thickness. For the sake of the sealant's processability, especially in preventing sagging, the viscosity is preferably 2 (mPa·s, 25°C) or higher, more preferably 5 (mPa·s, 25°C) or higher, and even more preferably 10 (mPa·s, 25°C) or higher. Furthermore, for the sake of the sealant's ease of penetration into the pores, it is 200 (mPa·s, 25°C) or lower, preferably 100 (mPa·s, 25°C) or lower, and even more preferably 50 (mPa·s, 25°C) or lower. By placing it within this range, the sealing performance (air tightness) is improved, and the processability is also excellent.

[0054] As a specific method for sealing pores, firstly, a sealing agent is applied to the joint by coating, spraying, or other means to obtain a coating film. At this time, to improve sealing (airtightness), pressure can be reduced on the opposite side of the joint where the sealing agent was applied. Pressure reduction can be performed before, simultaneously with, or after the sealing agent adheres to the joint surface. By reducing pressure in this way, the sealing agent can penetrate the pores of the joint without gaps, thus blocking the pores on the surface of the joint.

[0055] Next, the resulting coating is cured to form a sealing film. The curing method depends on the type of sealing agent. When using a solution of polymeric material or a suspension of inorganic microparticles as the sealing agent, drying at 100–300°C for 60–300 minutes is sufficient. When using a composition containing polymeric material and a crosslinking agent, heat curing or light curing can also be performed. Furthermore, when using organic or inorganic monomers or oligomers as the sealing agent, curing can be achieved by polymerizing these at 100–300°C for 30–180 minutes.

[0056] When using a silica film as a sealing film, a sealing process known as silicate oligomer treatment can be performed. The silicate oligomer treatment is performed, for example, as follows: First, a sealing agent containing a silicate oligomer, typically an alkoxysilane compound, is applied to the bonding portion. Examples of commercially available silicate oligomers of this type include MKCSilicate (registered trademark) MS-51, MS-56, MS-57, MS-56S (all manufactured by Mitsubishi Chemical Corporation, methyl silicate oligomers), Ethyl silicate 40, Ethyl silicate 48 (all manufactured by COLCOAT CO.,LTD., ethyl silicate oligomers), Silicate 40, Silicate 45 (Tama Chemical Industry), and EMS-485 (manufactured by COLCOAT CO.,LTD.), a mixed oligomer of methyl silicate and ethyl silicate. Next, by heating the obtained coating at 150–280°C for 30–180 minutes to carry out hydrolysis and condensation reactions using the sol-gel method, a silica film can be obtained.

[0057] When using silicone resin as a sealing film, a sealing agent containing an oligomer of alkoxyalkylsilane can be used. Examples of such sealing agents include Permeate HS-80, HS-90, HS-100, HS-200, HS-300, HS-330, HS-350, HS-360, and HS-820 (all manufactured by D&D CORPORATION). A silica film can be obtained by heating the coating obtained with the resin at 150–280°C for 30–180 minutes to perform a sol-gel hydrolysis and polycondensation reaction.

[0058] <Separation Membrane Module> As another embodiment, the separation membrane assembly has a composite of zeolite and inorganic porous support and dense components, and may also include a container with inlet and outlet ports, flanges, piping, etc. By placing the separation membrane module inside a high-pressure vessel, gases or solvents can be separated by applying pressure or by vacuum venting on the permeate side. Furthermore, the separation membrane module can also be used to separate substances simultaneously with a reaction.

[0059] <reactor> By placing the separation membrane assembly of this embodiment in the reactor, in a manufacturing method that utilizes a reaction in which a reverse reaction occurs, the original chemical equilibrium can be continuously shifted in a direction favorable to production. Therefore, the yield can be increased, concerns about breakage are reduced, and it can be used for a long time.

[0060] <Conditions of Use> When the conjugate of this embodiment is used in an organic chemical reaction process, the temperature is typically 100–450°C, preferably 200–350°C. It can also be used under high-temperature conditions of 150°C–500°C. Furthermore, the pressure is typically 0.5–8 MPa, preferably 2–6 MPa. It can also be used under high-pressure conditions of 0.5–10 MPa.

[0061] <<Second Implementation Method>> The second embodiment of the present invention is a joint body, which is formed by bonding a composite of zeolite and an inorganic porous support and a dense component through an inorganic glass, wherein the dense component is a metal component and the coefficient of thermal expansion of the inorganic glass is 30 × 10⁻⁶. -7 / K or higher and 90×10 -7 It has a temperature below / K and a softening point below 550℃.

[0062] Inorganic Glass The coefficient of thermal expansion of the inorganic glass involved in this embodiment is typically 30 × 10⁻⁶. -7 / K or higher, preferably 40×10 -7 / K or higher, preferably 45×10 -7 / K or higher, in addition, it is usually 90×10 -7 / K or less, preferably 80×10 -7 / K or less, preferably 75×10 -7 / K or below.

[0063] In this embodiment, the coefficient of thermal expansion of the inorganic glass is typically 60% or more, preferably 70% or more, more preferably 80% or more, and typically 200% or less, preferably 150% or less, more preferably 120% or less. Because the coefficient of thermal expansion of the inorganic glass is below the aforementioned upper limit, when the temperature is lowered after bonding at the melting temperature of the inorganic glass, internal stress is less likely to be generated around the joint, and cracks in the joint are suppressed. On the other hand, because the coefficient of thermal expansion of the glass is above the aforementioned lower limit, gaps are less likely to form between the composite and the dense component within the operating temperature range of the bond, and leakage of the target gas from these gaps to the refined gas side can be suppressed. Preferably, in the test method described in the Examples section of this specification, the resulting joint is preferably with an air permeability of 10 sccm or less, more preferably 8 sccm or less, and most preferably 5 sccm or less. Furthermore, preferably, even after adding 1 / 16 methanol and 1 / 16 demineralized water by volume relative to the internal volume in the autoclave, heating to 280°C for 1 hour, maintaining this state for 48 hours, allowing natural cooling, and drying at 120°C under normal pressure for 4 hours, the air permeability of the bonded joint is measured again. The air permeability is 10 sccm or less, more preferably 8 sccm or less, and most preferably 5 sccm or less. By satisfying conditions such as the coefficient of thermal expansion, even with longer-term methanol production, no problems will occur at the joint, making this method even more preferable.

[0064] When a separation assembly having the joint described in this embodiment is used in industry, it will repeatedly cycle between room temperature and operating temperature, and will also operate for extended periods at the operating temperature. Therefore, it is required that the joint formed by the inorganic glass does not leak the gas to be separated, even under these high temperature and high pressure conditions. By setting the coefficient of thermal expansion of the inorganic glass as described above, leakage of the gas to be separated can be suppressed.

[0065] The inorganic glass involved in this embodiment has a softening point of 550°C or less, preferably 530°C or less, and more preferably 480°C or less. Generally, the inorganic glass frit can be made to flow by calcining it at a temperature approximately 50°C above its softening point. Therefore, by keeping the softening point of the inorganic glass within the above-mentioned range, zeolite and inorganic glass can be chemically bonded at a relatively low temperature of around 600°C or less, and the inorganic glass can enter the pores of the composite, allowing the composite to be mechanically and firmly bonded to the dense component. Furthermore, since the bonding temperature is relatively low, damage to the zeolite due to heating during bonding is reduced. Moreover, since the bonding itself is performed at a low temperature, damage during cooling of the bonded portion is reduced, and improved properties and extended lifespan are also expected.

[0066] As for the inorganic glass, there are no particular limitations as long as it has the aforementioned coefficient of thermal expansion and softening point. Examples of components contained in the inorganic glass include SiO2, Al2O3, ZnO, P2O5, Bi2O3, BaO, TiO2, TeO2, V2O5, B2O3, SnO, and PbO. Among these, from the perspective of improving sealing performance, inorganic glasses containing B2O3 and / or SnO are particularly preferred. Specific examples of inorganic glasses containing B2O3 and / or SnO include SnO-P2O5 series glasses, Bi2O3-ZnO series glasses, Bi2O3-B2O3 series glasses, Bi2O3-B2O3-SiO2 series glasses, and Bi2O3-ZnO-B2O3 series glasses. Commercially available products that are inorganic glass materials include “FP-74”, “KP312E”, “FP-67”, “BNL115BB”, “ASF-1094”, “ASF-1098”, “ASF-1109” (all manufactured by AGC Corporation); “BF-0606”, “BF-0901” (all manufactured by Nippon Electric Glass Corporation); etc.

[0067] When inorganic glass contains SnO, its content is not particularly limited, but is usually less than 80% by mass, preferably less than 75% by mass, more preferably less than 70% by mass, and usually less than 10% by mass, preferably more than 20% by mass, more preferably more than 30% by mass. By ensuring the SnO content falls within this range, the fluidity of the glass can be adequately guaranteed, making it easy to achieve sufficient airtightness. The specific effects of adding SnO are not yet fully understood, but it is known to act as a reducing agent, suggesting that it may modify the oxide film on the surface of dense components or inhibit the increase in oxide film thickness during bonding processes, thereby improving airtightness.

[0068] On the other hand, when inorganic glass contains B2O3, its content is typically 25% by mass or less, preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 15% by mass or less. Furthermore, it is typically 1% by mass or less, preferably 2% by mass or more, and more preferably 3% by mass or more. Adding B2O3 improves its wettability with dense components, making it easier to enhance airtightness. On the other hand, a higher B2O3 content tends to increase the softening point, reducing the flexibility in mixing other components to maintain a softening point below 550°C. Therefore, it is preferable to select components within the aforementioned range. Furthermore, since B2O3 is soluble in water and alcohol, and there is a possibility of exposure to these substances under high temperature or high pressure conditions, it is preferable to select components below the aforementioned upper limit.

[0069] In addition, methods for quantifying the content of SnO and B2O3 include XRF (fluorescence X-ray analysis) and ICP (inductively coupled plasma atomic emission spectrometry).

[0070] There are no particular restrictions on the form of inorganic glass. Powdered glass frit, tablets formed by pressing glass frit, tablets used as sintered products of glass frit, and glass slurries formed by uniformly dispersing glass frit in organic solvents or binders can be used. In mass production of joints, tablet or slurry-like substances are particularly preferred due to their ability to improve production efficiency.

[0071] Furthermore, the inorganic glass in this embodiment is preferably inorganic glass with a lead (Pb) content of 10% by mass or less when converted to PbO, more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, particularly preferably 1% by mass or less, and most preferably 0% by mass. Lead content can also be determined by XRF (X-ray fluorescence analysis) and ICP (inductively coupled plasma atomic emission spectrometry).

[0072] In this embodiment, the zeolite, the inorganic porous support, and the composite of zeolite and inorganic porous support can be made of the same materials as in the first embodiment.

[0073] <Dense Components> The dense component is a part used to extract the separated gas to the outside, such as a pipe, and has a degree of density (fineness) to the extent that the gas to be processed does not leak from the component. In this invention, metal components are used. Examples of metals mentioned here are preferably materials that have both heat resistance and corrosion resistance, such as stainless steel, nickel-molybdenum-iron alloys (e.g., HASTELLOY (registered trademark)), Inconel (nickel-chromium-iron alloy), copper, copper alloys (brass, low-zinc brass, cupronickel), aluminum, aluminum alloys, titanium, etc., and Kovar (iron-cobalt-nickel alloy) is particularly preferred. The coefficient of thermal expansion of dense components is typically 30 × 10⁻⁶. -7 / K or higher and 200×10 -7 For values ​​below / K, the lower limit is preferably 35×10. -7 / K or higher, preferably 40×10 -7 / K or higher, further preferably 45×10 -7 / K or higher. The upper limit is preferably 150×10 -7 / K or less, more preferably 120×10 -7 Below / K, 85×10 is further preferred. -7 / K or below. By making the coefficient of thermal expansion of the dense component within the above range, the difference between its coefficient of thermal expansion and that of inorganic glass is smaller, thus ensuring good airtightness and durability. Furthermore, the coefficient of thermal expansion in this invention refers to the coefficient of linear expansion, which represents the proportion of change in the length of a solid as temperature increases. The method described in JIS Z 2285 (Metallic Materials), JIS R 1618 (Ceramics), etc., is followed. The coefficient of thermal expansion is typically measured within a range where the change in length is proportional to the change in temperature; in this specification, the coefficient of thermal expansion is typically a value measured at 30–250°C.

[0074] In this embodiment, the connection can also be made at both ends when the composite is a cylindrical support. For example, in a mixed gas separation process using a cylindrical zeolite membrane composite, separation is achieved by filling the outside of the cylindrical support with the zeolite membrane with mixed gas and applying pressure, or by vacuum degassing the inside. Therefore, one end can be sealed with a cap and a pipe connected to the other end, or pipes can be connected to both ends.

[0075] The method of joining a composite with a zeolite film on its surface to a cap made of dense components or to a pipe made of dense components with end structures similar to caps can be any method if it is a method that can join the composite and the cap with inorganic glass. For example, the following method can be used: filling the recess of the dense component with inorganic glass, placing the composite with a zeolite film on its surface on it, and then firing it under a load with a weight placed on top of the composite to join them.

[0076] Regarding the firing temperature for bonding the composite to the dense component using inorganic glass, it must be above the softening point of the inorganic glass used. Therefore, the firing temperature is typically above the softening point +10°C, preferably above the softening point +30°C, and more preferably above the softening point +50°C. Furthermore, to avoid thermal damage to the zeolite film, it is typically below 600°C, preferably below 580°C, and more preferably below 560°C. Additionally, the firing time after reaching the firing temperature is typically 5 to 90 minutes, preferably 10 minutes or more, more preferably 20 minutes or more, and more preferably 60 minutes or less, and more preferably 40 minutes or less.

[0077] The following text uses Figures 1-3 This section describes an example of a composite material formed by bonding zeolite with an inorganic porous support and a dense component using inorganic glass. like Figure 1 As shown, the composite 1 of zeolite and inorganic porous support, and the flange 11, can be directly joined by inorganic glass 4. In this embodiment, the risks of gas leakage and other problems associated with the deterioration of connections between components over time can be reduced. In this case, the flange 11 becomes a dense component made of metal. On the other hand, it can also be like Figure 2 As shown, the composite 1 of zeolite and inorganic porous support, and the piping 3 are joined only by the inorganic glass 4. Since the inorganic glass of this embodiment has high airtightness and durability, such a joint is possible. In this case, the piping 3 becomes a dense component made of metal parts. Figure 3 This is a cross-sectional schematic diagram illustrating an example of a zeolite-inorganic porous support composite 1 and a piping 3 joined together by an inorganic glass 4. The zeolite-inorganic porous support composite 1 is joined to the piping 3 by the inorganic glass 4. The piping 3 is joined in such a way that it covers the zeolite-inorganic porous support composite 1.

[0078] <Sealing film> In this embodiment, it is preferable that the joint between the composite and the dense component is covered by a sealing film. The joint may have micropores such as cracks and pinholes on its surface due to the calcination process of the inorganic glass used for bonding. Therefore, from the perspective of improving airtightness, it is preferable to perform a sealing treatment on the joint to block these micropores. Furthermore, it is also ideal to cover the joint with a sealing film because the sealing film formed by the sealing treatment can suppress deterioration and damage such as pinholes in the joint.

[0079] Examples of sealing agents that can form a sealing film include inorganic materials such as silica and various alumina; organic polymers such as silicone resins, epoxy resins, and fluorinated resins; and substances that may contain solvents or be solvent-free. In this embodiment, from the perspective of adhesion to inorganic glass and gas barrier properties, inorganic sealing agents, especially silica, are preferred. The amount of sealing agent applied can be appropriately determined according to the desired film thickness of the sealing film. For the sake of the processability of the sealing agent, especially in preventing sagging, the viscosity is preferably 2 (mPa·s, 25°C) or more, more preferably 5 (mPa·s, 25°C) or more, and even more preferably 10 (mPa·s, 25°C) or more. Furthermore, for the sake of easy penetration of the sealing agent into the pores, it is 200 (mPa·s, 25°C) or less, preferably 100 (mPa·s, 25°C) or less, and even more preferably 50 (mPa·s, 25°C) or less. By placing it within this range, airtightness is improved, and processability is also excellent.

[0080] As a specific method for sealing pores, firstly, a sealing agent is applied to the joint area by coating, spraying, or other means to obtain a coating film. At this time, to improve airtightness, pressure can be reduced on the opposite side of the joint area where the sealing agent is applied. Pressure reduction can be performed before, simultaneously with, or after the sealing agent adheres to the joint surface. By reducing pressure in this way, the sealing agent can penetrate the pores of the joint area without voids, thus blocking the pores on the surface of the joint area.

[0081] Next, the resulting coating is cured to form a sealing film. The curing method depends on the type of sealing agent. When using a solution of polymeric material or a suspension of inorganic microparticles as the sealing agent, drying at 100–300°C for 60–300 minutes is sufficient. When using a composition containing polymeric material and a crosslinking agent, heat curing or light curing can also be performed. Furthermore, when using organic or inorganic monomers or oligomers as the sealing agent, curing can be achieved by polymerizing these at 100–300°C for 30–180 minutes.

[0082] When using a silica film as a sealing film, a sealing process known as silicate oligomer treatment can be performed. The silicate oligomer treatment is performed, for example, as follows: First, a sealing agent containing a silicate oligomer, typically an alkoxysilane compound, is applied to the bonding portion. Examples of commercially available silicate oligomers of this type include MKCSilicate (registered trademark) MS-51, MS-56, MS-57, MS-56S (all manufactured by Mitsubishi Chemical Corporation, methyl silicate oligomers), Ethyl silicate 40, Ethyl silicate 48 (all manufactured by COLCOAT CO.,LTD., ethyl silicate oligomers), Silicate 40, Silicate 45 (Tama Chemical Industry), and EMS-485 (manufactured by COLCOAT CO.,LTD.), a mixed oligomer of methyl silicate and ethyl silicate. Next, by heating the obtained coating at 150–280°C for 30–180 minutes to carry out hydrolysis and condensation reactions using the sol-gel method, a silica film can be obtained.

[0083] When using silicone resin as a sealing film, a sealing agent containing an oligomer of alkoxyalkylsilane can be used. Examples of such sealing agents include Permeate HS-80, HS-90, HS-100, HS-200, HS-300, HS-330, HS-350, HS-360, and HS-820 (all manufactured by D&D CORPORATION). A silicone resin film can be obtained by heating the coating obtained by coating with it at 150–250°C for 30–180 minutes.

[0084] <Separation Membrane Module> As another embodiment, the separation membrane assembly has a composite of zeolite and inorganic porous support and dense components, and may also include a container with inlet and outlet ports, flanges, piping, etc. By placing the separation membrane module inside a high-pressure vessel, gases or solvents can be separated by applying pressure or by vacuum venting on the permeate side. Furthermore, the separation membrane module can also be used to separate substances simultaneously with a reaction.

[0085] <reactor> By placing the separation membrane assembly of this embodiment in the reactor, in a manufacturing method utilizing a reaction that can undergo a reversible reaction, the product yield can be increased by continuously removing the product and / or byproduct from the reactor, and concerns about breakage are reduced, allowing for long-term use.

[0086] <Conditions of Use> When the conjugate of this embodiment is used in an organic chemical reaction process, the temperature is typically 100–450°C, preferably 200–350°C. It can also be used under high-temperature conditions of 150°C–500°C. Furthermore, the pressure is typically 0.5–8 MPa, preferably 2–6 MPa. It can also be used under high-pressure conditions of 0.5–10 MPa.

[0087] <<Third Implementation Method>> The third embodiment of the present invention is a composite body formed by bonding a zeolite-inorganic porous support and a dense component using an inorganic adhesive, wherein the coefficient of thermal expansion of the inorganic adhesive after curing is 30 × 10⁻⁶. -7 / K~90×10 -7 / K.

[0088] Inorganic adhesives The inorganic adhesive used in this embodiment is characterized by its main component being inorganic substances, preferably oxides or nitrides. Therefore, it can maintain high airtightness and excellent durability even when used under high temperature and pressure and in contact with organic solvents or organic gases. Furthermore, the inorganic adhesive in this embodiment is a substance that bonds through a chemical reaction and does not revert to its original state when heated. Since inorganic adhesives can typically bond at temperatures below 200°C, they are virtually undamaged by the zeolite film, making them preferable. As an inorganic binder, substances with alumina, zirconium oxide, silica, magnesium oxide, zircon, graphite, aluminum nitride, and mixtures thereof as main components can be appropriately used. The coefficient of thermal expansion of the inorganic binder depends approximately on the coefficient of thermal expansion of the main component and can be adjusted by adding other additives. When using the above-mentioned main components, it is preferable because it is easy to make the coefficient of thermal expansion within the preferred range described below. The coefficient of thermal expansion of the inorganic adhesive used in this embodiment is typically 30 × 10⁻⁶ after curing. -7 / K~90×10 -7 / K, the lower limit is preferably 35×10 -7 / K or higher, preferably 45×10 -7 / K or higher, further preferably 55×10 -7 / K or higher. The preferred upper limit is 88×10. -7 / K, more preferably 85×10 -7 Below / K, 82×10 is further preferred. -7 / K or below. Furthermore, the difference in the coefficients of thermal expansion between the inorganic binder and the dense component is preferably 50 × 10⁻⁶. -7 / K or less, preferably 40×10 -7 / K or less, preferably 30×10 -7 / K or less, preferably 15×10 -7 / K or below. In the test methods described in the Examples section of this specification, the air permeability of the composite obtained by bonding the composite to the dense component with an inorganic adhesive like this is preferably 100 sccm or less, more preferably 50 sccm or less, further preferably 20 sccm or less, and most preferably 10 sccm or less. Furthermore, even after adding 1 / 16 of methanol and 1 / 16 of demineralized water relative to the internal volume in the autoclave, heating to 280°C for 1 hour, maintaining this state for 48 hours, allowing natural cooling, and drying at 120°C under normal pressure for 4 hours, the air permeability of the joint is measured again. The air permeability of the joint is preferably 100 sccm or less, more preferably 50 sccm or less, further preferably 20 sccm or less, and most preferably 10 sccm or less. By satisfying conditions such as the coefficient of thermal expansion, even with prolonged methanol production, problems will not occur at the joint when the separation membrane assembly with the joint is installed in the methanol synthesis reactor, making this method even more preferable.

[0089] Furthermore, the inorganic binder used in this embodiment preferably contains a metal alkoxide. The specific effects of adding metal alkoxides are not yet clear, but it is speculated that they react with the oxide layer on the surface of dense components to improve the bonding strength, thus making it less prone to cracks and pinholes.

[0090] Examples of the aforementioned metal alkoxides include alkali metal alkoxides such as lithium methoxide, lithium ethoxide, sodium methoxide, sodium ethoxide, potassium methoxide, and potassium ethoxide; alkaline earth metal alkoxides such as magnesium methoxide, magnesium ethoxide, calcium methoxide, and calcium ethoxide; alkoxides of Group 13 elements such as boron methoxide, boron ethoxide, aluminum methoxide, aluminum ethoxide, aluminum propoxide, aluminum butoxide, gallium methoxide, and gallium ethoxide; alkoxides of Group 14 elements such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, germanium methoxide, germanium ethoxide, tin methoxide, and tin ethoxide; alkoxides of Group 4 elements such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium butoxide, zirconium methoxide, zirconium ethoxide, zirconium propoxide, zirconium butoxide, hafnium methoxide, and hafnium ethoxide; and alkoxides of Group 5 elements such as vanadium methoxide, vanadium ethoxide, niobium methoxide, niobium ethoxide, tantalum methoxide, and tantalum ethoxide. Furthermore, oligomers of the alkoxides listed above can also be cited. Among these, aluminum alkoxides such as aluminum methoxide, aluminum ethoxide, aluminum propoxide, and aluminum butoxide are preferred due to their ease of forming cross-linked structures and their readily available availability; silanols such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, and methyltriethoxysilane; titanium alkoxides such as titanium methoxide, titanium ethoxide, titanium propoxide, and titanium butoxide; zirconium alkoxides such as zirconium methoxide, zirconium ethoxide, zirconium propoxide, and zirconium butoxide; and their oligomers are also preferred. Among these, aluminum methoxide, aluminum ethoxide, aluminum propoxide, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, titanium ethoxide, titanium propoxide, titanium butoxide, zirconium ethoxide, zirconium propoxide, zirconium butoxide, and their oligomers are even more suitable.

[0091] Furthermore, the content of metal alkoxides in the inorganic binder is typically 0.01 to 5% by mass, preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 3% by mass or less, more preferably 1% by mass or less. When it is 0.01% by mass or more, a significant improvement in physical properties can be observed. On the other hand, by keeping it at 5% by mass or less, the increase in specific gravity can be suppressed, which is also advantageous in terms of cost, and it is also easy to maintain a high impact strength. Inorganic adhesives suitable for use in this embodiment may be used, such as “TB3732” manufactured by ThreeBond Co., Ltd., which is commercially available.

[0092] In this embodiment, the zeolite, the inorganic porous support, and the composite of zeolite and inorganic porous support use the same materials as in the first embodiment.

[0093] <Dense Components> A dense component is a component that possesses a degree of tightness (fineness) to the extent that the gas supplied to the reaction or the gas produced after the reaction does not leak out of the component. There are no particular limitations on components possessing such tightness, and metals are typically used. Examples of metals mentioned here include stainless steel, ceramics such as alumina and zirconium oxide, and alloys such as Kovar. The coefficient of thermal expansion of dense components is typically 30 × 10⁻⁶. -7 / K~200×10 -7 / K, the lower limit is preferably 35×10 -7 / K or higher, preferably 40×10 -7 / K or higher, further preferably 45×10 -7 / K or higher. The upper limit is preferably 150×10 -7 / K or less, more preferably 120×10 -7 Below / K, 85×10 is further preferred. -7 / K or less. By making the coefficient of thermal expansion of the dense component within the above range, the difference between its coefficient of thermal expansion and that of the inorganic binder is as small as, for example, 50 × 10⁻⁶. -7 Below / K, good sealing (air tightness) and durability can be ensured. Furthermore, the coefficient of thermal expansion in this invention refers to the coefficient of linear expansion, which represents the proportion of change in the length of a solid as temperature increases. In this specification, the coefficient of thermal expansion is the average value between 30°C and 300°C. The determination of the coefficient of thermal expansion is performed according to the methods described in JIS Z2285 (Metallic Materials), JIS R1618 (Ceramics), etc.

[0094] In this embodiment, the connection can also be made at both ends when the composite is a cylindrical support. For example, in a mixed gas separation process using a cylindrical zeolite membrane composite, separation is achieved by filling the outside of the cylindrical support with the zeolite membrane with mixed gas and applying pressure, or by vacuum degassing the inside. Therefore, one end can be sealed with a cap and a pipe connected to the other end, or pipes can be connected to both ends.

[0095] The method of joining a composite with a zeolite film on its surface to a cap made of dense components or to a pipe made of dense components with a similar cap end structure can be any method if it is a method that can join the composite and the cap with an inorganic adhesive. For example, the following method can be used: applying an inorganic adhesive to the side portion of the composite and the portion in contact with the cap in advance, and joining the composite while rotating the cap on the composite and smoothing the joint surface.

[0096] After the composite is bonded to the dense component using an inorganic binder, it is left at room temperature for 1 to 24 hours as needed, followed by firing to achieve bonding. In this embodiment, room temperature refers to 15 to 30°C. The firing temperature for bonding is typically 80–200°C, preferably 90°C or higher, more preferably 100°C or higher, and further preferably 180°C or lower, more preferably 150°C or lower. The firing time for bonding is typically 10–300 minutes, preferably 30 minutes or higher, more preferably 60 minutes or higher, and further preferably 180 minutes or lower, more preferably 120 minutes or lower.

[0097] The following text uses Figures 1-3 This illustrates an example of a composite material and a dense component formed by bonding zeolite to an inorganic porous support using an inorganic binder. like Figure 1 As shown, the composite 1 of zeolite and inorganic porous support, and flange 11 can be directly bonded by inorganic adhesive 4. In this embodiment, the risks of gas leakage and other problems associated with the deterioration of connections between components over time can be reduced. In this case, flange 2 becomes a dense component. On the other hand, such as Figure 2 As shown, the zeolite and the inorganic porous support composite 1 and the piping 3 can also be joined solely by the inorganic adhesive 4. Since the inorganic adhesive of this embodiment has high airtightness and durability, such a joint is possible. In this case, the piping 3 becomes a dense component. Figure 3 This is a cross-sectional schematic diagram illustrating an example of a zeolite-inorganic porous support composite 1 and a piping 3 bonded together by an inorganic adhesive 4. The zeolite-inorganic porous support composite 1 is bonded to the piping 3 by the inorganic adhesive 4. The piping 3 is bonded in a manner that covers the zeolite-inorganic porous support composite 1. Furthermore, the "joint body" of the present invention refers to a composite of zeolite and inorganic porous support and a dense component joined together, which is a component that can be removed when the performance of the composite deteriorates and it is replaced. However, when there is no such removal mechanism, for example when it is installed in a reactor such as a methanol synthesis reactor, it includes a dense component that exists inside the reactor.

[0098] <Sealing film> In this embodiment, it is preferable that the joint portion between the composite and the dense component is covered by a sealing film. The joint portion may exhibit micropores such as cracks and pinholes on its surface due to the calcination of the inorganic adhesive used for bonding. Therefore, from the perspective of improving sealing (air tightness), it is preferable to perform a sealing treatment on the joint portion to block these micropores. Furthermore, it is also ideal to cover the joint portion with a sealing film because the sealing film formed by the sealing treatment can suppress deterioration and damage such as pinholes in the joint portion.

[0099] Examples of sealing agents that can form a sealing film include inorganic materials such as silica and various alumina; and organic polymers such as silicone resins, epoxy resins, and fluorinated resins. These sealing agents may contain solvents or be solvent-free. In this embodiment, inorganic sealing agents, particularly silica, are preferred from the perspective of good adhesion to inorganic adhesives and gas barrier properties. Furthermore, silicone resins may also be suitable for forming a dense film. The amount of sealing agent applied can be appropriately determined according to the desired film thickness. For the processability of the sealing agent, especially for preventing sagging, the viscosity is preferably 2 (mPa·s, 25°C) or more, more preferably 5 (mPa·s, 25°C) or more, and even more preferably 10 (mPa·s, 25°C) or more. Furthermore, the angle at which the sealing agent easily penetrates the pores is preferably 200 mPa·s at 25°C or less, more preferably 100 mPa·s at 25°C or less, and even more preferably 50 mPa·s at 25°C or less. By placing it within this range, the sealing performance is improved, and the processability is also excellent.

[0100] As a specific method for sealing pores, firstly, a sealing agent is applied to the joint by coating, spraying, or other means to obtain a coating film. At this time, to improve sealing (airtightness), pressure can be reduced on the opposite side of the joint where the sealing agent was applied. Pressure reduction can be performed before, simultaneously with, or after the sealing agent adheres to the joint surface. By reducing pressure in this way, the sealing agent can penetrate the pores of the joint without gaps, thus blocking the pores on the surface of the joint.

[0101] Next, the resulting coating is cured to form a sealing film. The curing method depends on the type of sealing agent. When using a solution of polymeric material or a suspension of inorganic microparticles as the sealing agent, drying at 100–300°C for 60–300 minutes is sufficient. When using a composition containing polymeric material and a crosslinking agent, heat curing or light curing can also be performed. Furthermore, when using organic or inorganic monomers or oligomers as the sealing agent, curing can be achieved by polymerizing these at 100–300°C for 30–180 minutes.

[0102] When using a silica film as a sealing film, a sealing process known as silicate oligomer treatment can be performed. The silicate oligomer treatment is performed, for example, as follows: First, a sealing agent containing a silicate oligomer, typically an alkoxysilane compound, is applied to the bonding portion. Examples of commercially available silicate oligomers of this type include MKCSilicate (registered trademark) MS-51, MS-56, MS-57, MS-56S (all manufactured by Mitsubishi Chemical Corporation, methyl silicate oligomers), Ethyl silicate 40, Ethyl silicate 48 (all manufactured by COLCOAT CO.,LTD., ethyl silicate oligomers), Silicate 40, Silicate 45 (Tama Chemical Industry), and EMS-485 (manufactured by COLCOAT CO.,LTD.), a mixed oligomer of methyl silicate and ethyl silicate. Next, by heating the obtained coating at 150–280°C for 30–180 minutes to carry out hydrolysis and condensation reactions using the sol-gel method, a silica film can be obtained.

[0103] When using silicone resin as a sealing film, a sealing agent containing an oligomer of alkoxyalkylsilane can be used. Examples of such sealing agents include Permeate HS-80, HS-90, HS-100, HS-200, HS-300, HS-330, HS-350, HS-360, and HS-820 (all manufactured by D&D CORPORATION). A silicone resin film can be obtained by heating the coating obtained by coating with it at 100–250°C for 30–180 minutes.

[0104] <Separation Membrane Module> As another embodiment, the separation membrane assembly has a composite of zeolite and inorganic porous support and dense components, and may also include a container with inlet and outlet ports, flanges, piping, etc. The separation membrane assembly is placed inside a high-pressure vessel, and gases or solvents can be separated by applying pressure or by vacuum venting on the permeation side. In addition, the separation membrane module can also be used in a manner that allows separation to occur simultaneously with the reaction. <reactor> By placing the separation membrane assembly of this embodiment in the reactor, in a manufacturing method that utilizes a reaction in which a reverse reaction occurs, the original chemical equilibrium can be continuously shifted in a direction favorable to production. Therefore, the yield can be increased, concerns about breakage are reduced, and it can be used for a long time.

[0105] <Conditions of Use> When the conjugate of this embodiment is used in an organic chemical reaction process, the temperature is typically 100–450°C, preferably 200–350°C. It can also be used under high-temperature conditions of 150°C–500°C. Furthermore, the pressure is typically 0.5–8 MPa, preferably 2–6 MPa. It can also be used under high-pressure conditions of 0.5–10 MPa.

[0106] <<Fourth Implementation Method>> The fourth embodiment of the present invention is a methanol production method, in which a raw material gas is reacted in a reactor in the presence of a catalyst to obtain methanol, wherein the raw material gas contains at least: hydrogen, and carbon monoxide and / or carbon dioxide. The feed gas contains hydrogen (H2) and carbon monoxide and / or carbon dioxide (collectively referred to as CO). x There are no particular restrictions on the content ratio of H2:CO. x The volume ratio is 4:6 to 9:1, preferably 5:5 to 8:2.

[0107] The raw material gas may also contain H2 and CO. x Other gases. As H2 and CO x Other gases include CH4, C2H4, C2H6, C3H6, C3H8, C4H8, and C4H. 10 H2O, etc., H2 and CO x The content of other gases is usually below 50% by volume.

[0108] Known catalysts can be used when producing methanol from feedstock gases, such as copper-based catalysts (copper-zinc catalysts, copper-chromium catalysts), zinc-based catalysts, chromium-based catalysts, aluminum-based catalysts, etc.

[0109] In this embodiment, a methanol selectively permeable membrane, bonded to a dense component by a bonding material, is provided inside the aforementioned methanol reactor. The bonding material is primarily composed of inorganic oxides and has a linear expansion coefficient of 30 × 10⁻⁶. -7 / K or higher and 90×10 -7 / K and below. This matter is explained using accompanying drawings. Furthermore, the linear expansion rate of the bonding material in this specification refers to the linear expansion rate of the bonding material after bonding (after firing), representing the proportion of change in the solid along its length as the temperature increases. It can be performed according to the methods described in JIS Z 2285 (metallic materials), JIS R 1618 (ceramics), etc. In this specification, the linear expansion rate is the average value over a temperature range of 30℃ to 300℃.

[0110] Figure 4 This is a cross-sectional schematic diagram illustrating one embodiment of the reactor of the present invention. Reactor 10 has a feed inlet a, a permeable gas outlet b, and a non-permeable gas outlet c. Since the methanol formation reaction takes place under high temperature and pressure, it is constructed of a material capable of withstanding such an environment. Although only one of inlet a, outlet b, and outlet c is shown in the figure, multiple outlets may also exist. The reactor 10 is equipped with a zeolite membrane composite 1, which serves as a methanol selective permeation membrane. There are no particular restrictions on the type of methanol selective permeation membrane if it can selectively permeate methanol; zeolite membranes are typically used. Details regarding the zeolite membrane composite are described later.

[0111] The zeolite membrane composite 1 is formed by forming a zeolite membrane on a porous support. The shape of the porous support is not limited to tubular; it can also be columnar, hollow columnar, or hollow honeycomb-shaped. One end of the zeolite membrane composite 1 is sealed by a cap 2, and the other end is connected to a pipe 3. The connection between the pipe 3 and the zeolite composite 1, as well as the connection between the cap 2 and the zeolite composite 1, can be achieved using a bonding material described later. The connection method of the zeolite membrane composite is not limited to the above. For example, it can also be a method where both ends are connected to the pipe, allowing gas to flow through the inside.

[0112] A catalyst 13 is arranged around the tubular zeolite membrane composite 1. The feed gas fed through inlet a contacts the catalyst 13, promoting methanol production. Furthermore, by permeating the generated methanol through the zeolite membrane of the zeolite membrane composite 1, methanol of higher purity can be obtained. Moreover, by selectively permeating methanol through the zeolite composite 1, the methanol concentration in the gas contacting the catalyst 13 is reduced, further promoting methanol production.

[0113] The other end of pipe 3 is connected to the permeate gas outlet b of the reactor, supplying methanol that has passed through the zeolite membrane of the zeolite membrane composite 1 to the permeate gas outlet b. Alternatively, the zeolite membrane composite 1 can be directly connected to the permeate gas outlet b of the reactor without going through pipe 3.

[0114] In this embodiment, the methanol selectively permeable membrane is bonded to a dense component via a bonding material, the bonding material being primarily composed of inorganic oxides with a linear expansion coefficient of 30 × 10⁻⁶. -7 / K or higher and 90×10 -7 / K or below. As an inorganic oxide, a suitable substance that can be used as an inorganic binder can be selected. The inorganic adhesive referred to here is a substance that bonds through chemical reaction and does not revert to its original state when heated. Inorganic adhesives are preferred because they can typically bond at temperatures below 200°C, thus causing minimal damage to the zeolite film. Inorganic glass can also be used. Examples of inorganic oxides include alumina, titanium dioxide, zirconium oxide, silicon dioxide, and magnesium oxide. Examples of inorganic glasses include those containing SiO2, Al2O3, ZnO, P2O5, Bi2O3, BaO, TiO2, TeO2, V2O5, B2O3, and SnO; lead-free inorganic glasses are preferred. Furthermore, the main component refers to the component with the highest content (by mass) among all components constituting the bonding material, typically 50% or more by mass, but also 70% or more by mass, 80% or more by mass, or 90% or more by mass. As a further preferred condition, the softening point temperature is below 550°C. Bonding is achieved by cooling the glass after it has been heated to a temperature approximately 50°C above its softening point temperature. Therefore, if the material has a softening point temperature greater than 550°C, the zeolite will be damaged, and thus this is not preferred. This phenomenon occurs because the separation membrane used in the zeolite of this invention is a methanol-selective membrane that allows methanol with a large molecular size to pass through easily but allows smaller molecules such as carbon dioxide to pass through poorly. Therefore, when exposed to temperatures above 600°C, there is a concern that the surface state of the zeolite may change, reducing its methanol selectivity.

[0115] The bonding material has a linear expansion rate of 30 × 10⁻⁶. -7 / K or higher and 90×10 -7 Below a certain K value, the adhesion between the methanol selectively permeable membrane and dense components is improved, giving it good sealing properties and durability. The linear expansion coefficient of the bonding material is preferably 40 × 10⁻⁶. -7 / K or higher, and preferably 80×10 -7 / K or below. The linear expansion rate of the bonding material largely depends on the linear expansion rate of the main component and can be adjusted by mixing in other additives. To achieve a linear expansion rate of 30 × 10⁻⁶... -7 / K or higher and 90×10 -7 For components with a K content below a certain level, alumina, zirconium oxide, silicon dioxide, graphite, P2O5, Bi2O3, SnO, etc., can be used as the main components.

[0116] Commercially available bonding materials can also be used, such as "TB3732" manufactured by ThreeBond Co., Ltd., "Aron Ceramic D" and "Aron Ceramic E" manufactured by Toa Synthetic Co., Ltd., "FP-74", "KP312E", "FP-67", "BNL115BB", "ASF-1094", "ASF-1098", and "ASF-1109" manufactured by AGC Co., Ltd., and "Ceramabond 552" manufactured by Aremco Products Inc.

[0117] A dense component bonded to a methanol selectively permeable membrane by a bonding material is a component with a degree of tightness (fineness) that prevents leakage of the gas supplied to the reaction or the gas after the reaction from the component. Examples include caps that seal the ends of tubular components and piping connected to the ends of tubular components. There are no particular limitations on components with such tightness, and metals are typically used. Examples of metals mentioned here include stainless steel, ceramics such as alumina and zirconium oxide, and alloys such as Kovar alloys.

[0118] In this embodiment, the dense component preferably has a linear expansion rate of 30 × 10⁻⁶. -7 / K or above 200×10 -7 / K or below. By making the linear expansion rate of the dense component within the above range, the difference in linear expansion rate with that of the bonding material can be reduced, ensuring good sealing and durability. Furthermore, the difference in the linear expansion rates between the bonding material and the dense component is preferably 50 × 10⁻⁶. -7 / K or less, preferably 40×10 -7 / K or less, preferably 30×10 -7 / K or less. When the difference in linear expansion rates between the bonding material and the dense component is small, bonding failures caused by material shrinkage during the sintering of the bonding material can be suppressed.

[0119] The following text uses Figures 5-7 This illustrates an example of a zeolite membrane composite that serves as a methanol permeation membrane and a dense component, which are bonded together using a bonding material. Figure 5 This is a cross-sectional schematic diagram illustrating an example of a zeolite membrane composite 1 bonded to a dense component via a bonding material. The zeolite membrane composite 1 is bonded to a pipe 3 via a bonding material 4. The pipe 3 is bonded in a manner that covers the zeolite membrane composite 1. On the other hand, such as Figure 6 As shown, the zeolite membrane composite 1 and the piping 3 can also be joined solely by a bonding material. Since the bonding material of this embodiment possesses high sealing performance and durability, such a joint is possible.

[0120] In addition, such as Figure 7 As shown, the zeolite membrane composite 1 can also be directly bonded to the reactor 10 via the bonding material 4. In this manner, since there is no piping involved, the cost of manufacturing the equipment can be reduced, and the risks of gas leakage due to the deterioration of the connection between components over time can also be reduced.

[0121] The methanol-selective permeable membrane in this embodiment is typically a zeolite membrane, but there are no particular limitations on the type of membrane that can selectively permeate methanol; various porous membranes, various MOFs (metal-organic frameworks), etc., can be used. In one embodiment, the zeolite membrane is formed on a porous support component such as alumina and can be used as a zeolite membrane composite.

[0122] The main zeolite constituting the zeolite film is preferably a zeolite containing a small-pore structure with oxygen rings of twelve or fewer or six or more members. The 'n' value in the context of zeolites with n-membered oxygen rings refers to the pores containing the largest number of oxygen atoms, formed by oxygen and T elements (elements other than oxygen in the framework) that constitute the zeolite framework. For example, MOR-type zeolites, in the presence of pores with 12-membered and 8-membered oxygen rings, are considered zeolites with 12-membered oxygen rings.

[0123] Examples of zeolites with a small-pore structure containing oxygen rings of twelve or fewer members or more members include those coded by the International Zeolite Association (IZA): AEI, AEL, AFI, AFG, ANA, ATO, BEA, BRE, CAS, CDO, CHA, CON, DDR, DOH, EAB, EPI, ERI, ESV, EUO, FAR, FAU, FER, FRA, HEU, GIS, GIU, GME, GOO, ITE, KFI, LEV, LIO, LOS, LTA, LTL, LTN, MAR, MEP, MER, MEL, MFI, MON, MOR, MSO, MTF, MTN, MTW, MWW, NON, NES, OFF, PAU, PHI, RHO, RTE, RTH, RUT, SGT, OD, STI, STT, TOL, TON, TSC, UFI, VNI, WEI, YUG, etc. Preferably, one of these is selected arbitrarily. Furthermore, zeolites are particularly suitable for use in this invention through selective adsorption, rather than through simple molecular sieves (i.e., sieves based solely on molecular size differences). This selective adsorption is used for purposes such as allowing larger molecules to pass through or separating substances of similar size. More preferably, separation is achieved through selective adsorption on the zeolite surface. The selective adsorption capacity of such zeolites decreases at higher temperatures, thus allowing the effects of this invention to be more significantly realized.

[0124] Because zeolites lack flexibility, they are fabricated as supports on certain substrates during film formation. The supports are porous, allowing gas molecules to penetrate them; for example, they have a large number of interconnected, three-dimensional micropores. As the material constituting the support, it is preferred to be a chemically stable material that does not react with the gas being treated and has excellent mechanical strength. Specifically, materials such as various alumina, silicon dioxide, silicon dioxide-alumina, mullite, cordierite, zirconium oxide and other oxide ceramics, silicon carbide, carbon, glass, etc. can be used. The shape of the support varies depending on the application of the zeolite membrane. In particular, zeolite membranes on cylindrical supports are suitable for batch processes, circulation processes (including recycling processes) due to their high strength in withstanding external pressure.

[0125] In this embodiment, a zeolite film composite with a zeolite film formed on a support can be used. For example, a cylindrical support is prepared, and zeolite microcrystals are first loaded into small holes. Loading methods include impregnation, friction, suction, and immersion. These microcrystals act as nuclei during the growth of the crystals constituting the zeolite film, and are also called seed crystals. The zeolite growth can be performed using hydrothermal synthesis, similar to zeolite synthesis.

[0126] The thickness of the zeolite membrane in the zeolite membrane composite is not particularly limited, but is typically 0.1 μm or more, preferably 0.5 μm or more, and also typically 50 μm or less, preferably 20 μm or less. By making the membrane thickness above the specified value, sufficient compactness can be obtained, maintaining high membrane selectivity. Furthermore, by making the membrane thickness below the specified value, sufficient gas permeation can be obtained.

[0127] In this embodiment, methanol is obtained by reacting a feed gas containing at least hydrogen and carbon monoxide and / or carbon dioxide in a reactor in the presence of a catalyst. The reaction conditions are not particularly limited, but a reaction temperature of 200°C or higher and 300°C or lower is preferred. Furthermore, the reaction temperature refers to the temperature inside the reactor. By maintaining a reaction temperature above 200°C, the reaction rate is increased, and the productivity is improved. By maintaining a reaction temperature below 300°C, the chemical equilibrium of the reaction is favorable for obtaining methanol, thus increasing the conversion rate even with a slight decrease in membrane performance. In addition, the tolerance range for the heat resistance required of the bonding materials is also increased.

[0128] The methanol obtained through the above reaction is recovered from the reactor's permeate gas outlet by passing it through a methanol selective permeation membrane inside the reactor. The pressure inside the reactor when the generated methanol passes through the methanol selective permeation membrane, i.e., the pressure (gauge pressure) on the gas supply side of the methanol selective permeation membrane in the reactor, is preferably 1 MPaG or more, more preferably 2 MPaG or more, more preferably 8 MPaG or less, and more preferably 5 MPaG or less. By maintaining the pressure within a suitable range, the limitation of reaction equilibrium can be reduced, and the reaction rate can be increased, making it easier to achieve higher productivity. In addition, the increase in reactor manufacturing costs and feed gas pressurization costs caused by excessive pressure can be suppressed. Furthermore, within the reaction vessel, the methanol partial pressure (absolute pressure) on the gas supply side of the methanol selective permeation membrane is preferably 0.1 MPaA or more, more preferably 0.2 MPaA or more, more preferably 6 MPaA or less, and more preferably 5 MPaA or less. By maintaining the methanol partial pressure within this range, a sufficient amount of methanol permeates through the membrane, maximizing the membrane's effectiveness. On the other hand, if it is within this range, the durability and sealing required for the joints will not be unnecessarily increased, allowing for simple and large-scale jointing. The gauge pressure within the reactor described above can be measured using a pressure gauge located within the reactor. Furthermore, the absolute pressure of methanol within the reactor varies from upstream to downstream; here, the absolute pressure of methanol within the reactor is taken as the analytical results of the reactor outlet gas composition obtained from gas chromatography and the value calculated using gauge pressure.

[0129] <<Fifth Implementation Method>> A fifth embodiment of the present invention is an alcohol manufacturing apparatus for synthesizing an alcohol by reacting a raw material containing at least hydrogen and carbon monoxide and / or carbon dioxide in the presence of a catalyst. The apparatus comprises: a reactor having an alcohol-selective permeable membrane with zeolite, a heat recovery device for recovering at least a portion of the reaction heat from the reactor, and a heat supply device for supplying the heat recovered by the heat recovery device. Furthermore, as an alcohol manufacturing method, a synthesis step is included in which a raw material containing at least hydrogen and carbon monoxide and / or carbon dioxide is reacted in the presence of a catalyst to synthesize an alcohol. Another embodiment of the fifth embodiment of the present invention includes a separation and recovery step in which the obtained alcohol is separated and recovered using an alcohol-selective permeable membrane with zeolite in the reactor, and a heat recovery step in which at least a portion of the reaction heat generated in the synthesis step is recovered from the reactor. The separation and recovery step is performed simultaneously with the heat recovery step.

[0130] The following describes in detail representative embodiments for implementing the fifth embodiment; however, the present invention may be implemented in various modifications without departing from its spirit.

[0131] One embodiment of the present invention is an alcohol manufacturing apparatus for synthesizing alcohols by reacting a raw material containing at least hydrogen and carbon monoxide and / or carbon dioxide in the presence of a catalyst. The manufacturing apparatus comprises: a reactor having an alcohol-selective permeable membrane with zeolite, a heat recovery device for recovering at least a portion of the heat of reaction from the reactor, and a heat supply device for supplying the heat recovered by the heat recovery device.

[0132] The feed gas contains hydrogen (H2) and carbon monoxide and / or carbon dioxide (collectively referred to as CO). x There are no particular restrictions on the content ratio of H2:CO. x The volume ratio is typically 4:6 to 9:1, preferably 5:5 to 8:2.

[0133] The feed gas may also contain H2 and CO. x Other gases. As H2 and CO x Other gases include CH4, C2H4, C2H6, C3H6, C3H8, C4H8, and C4H. 10 H2O, etc., H2 and CO x The content of other gases is usually below 50% by volume.

[0134] Preheated raw materials are introduced into a reactor, where they are synthesized into alcohols by a catalyst placed in the reactor. The alcohols can be lower alcohols with 1 to 4 carbon atoms, preferably alcohols with 1 to 3 carbon atoms, and most preferably methanol.

[0135] For catalysts used in the production of alcohols from feedstock gases, known catalysts can be used, such as copper-based catalysts (copper-zinc catalysts, copper-chromium catalysts), zinc-based catalysts, chromium-based catalysts, aluminum-based catalysts, etc.

[0136] The synthesis of alcohols via catalyst is an equilibrium reaction. This equilibrium reaction mainly involves the following three reactions to produce alcohols (methanol). 3H₂ + CO₂ → CH₃OH + H₂O …… Equation 1 2H₂ + CO → CH₃OH …… Equation 2 CO2 + H2 → CO + H2O …… Equation 3

[0137] In the reaction to synthesize alcohols, the yield of alcohols can be increased by using an alcohol-selective permeable membrane with zeolite to remove the alcohol (methanol in the above formula). Furthermore, in this invention, a device for recovering the heat of reaction (heat recovery device) is provided in the reactor where the reaction takes place. This prevents excessive temperature rise within the reactor and inhibits the reaction from shifting towards a direction where the alcohol is more easily decomposed. Therefore, it is preferable to control the temperature within the reactor. The temperature within the reactor is typically 200°C or higher, preferably 210°C or higher, more preferably 220°C or higher, and also typically 300°C or lower, preferably 290°C or lower, more preferably 270°C or lower. Any combination of these upper and lower limits is also possible. This temperature is the temperature of the gas within the reactor and can be determined by measuring the temperature of the mixture of unreacted feed gas and alcohol discharged from the reactor. There are no particular limitations on the device for recovering the heat of reaction; heat exchangers, steam generators, etc., can be used.

[0138] In alcohols separated by an alcohol selective permeation membrane, since the raw materials are inevitably mixed in, the alcohol can be liquefied by lowering the temperature of the alcohol passing through the membrane, thus separating it from unreacted hydrogen, carbon dioxide, and / or carbon monoxide. Alternatively, the reactor may be equipped with a line that does not pass through the alcohol selective permeation membrane. Since this line can also discharge unreacted raw materials and alcohol, the alcohol can be liquefied by lowering the temperature, similar to the gas passing through the membrane, thus separating it from unreacted hydrogen, carbon dioxide, and / or carbon monoxide. This process is a gas-liquid separation, and the temperature of the gas-liquid separation varies depending on the alcohol obtained. For methanol, it is typically below 60°C, preferably below 50°C, and more preferably below 40°C.

[0139] The unreacted raw materials recovered in this way can be mixed with new raw materials, preheated again, and then introduced into the reactor. There are no particular limitations on the preheating device for the raw materials before they are introduced into the reactor; by using the heat recovery device described above to recover the heat of reaction, the raw materials can be preheated, thus effectively utilizing thermal energy. In addition to preheating raw materials, other uses of recovered thermal energy include heating for product refining, heating to bring products to a temperature suitable for the next process, generating steam for use in the process, and using the generated steam to generate electricity. In this invention, devices that utilize the energy obtained from the heat recovery device in the process, as exemplified above, are collectively referred to as heat supply devices.

[0140] (Description of the apparatus) use Figure 9 An example of the apparatus of this embodiment will be described. Figure 9 This is a cross-sectional schematic diagram illustrating an example of the reactor in this embodiment. Reactor 10 has a feed inlet a, a permeable gas outlet b, and a non-permeable gas outlet c. Since the methanol formation reaction takes place under high temperature and pressure, it is constructed of a material capable of withstanding such an environment. Although only one of inlet a, outlet b, and outlet c is shown in the figure, multiple outlets may also exist. The reactor 10 is equipped with a zeolite membrane complex 1, which serves as an alcohol-selective permeation membrane. There are no particular restrictions on the type of alcohol-selective permeation membrane if it can selectively permeate alcohols; zeolite membranes are typically used. Details regarding the zeolite membrane complex will be provided later.

[0141] The zeolite membrane composite 1 is formed by forming a zeolite membrane on a porous support. The shape of the porous support is not limited to tubular; it can also be columnar, hollow columnar, or hollow honeycomb-shaped. One end of the zeolite membrane composite 1 is sealed by a cap 2, and the other end is connected to a pipe 3. The connection between the pipe 3 and the zeolite composite 1, as well as the connection between the cap 2 and the zeolite composite 1, can be achieved using a bonding material described later. The connection method of the zeolite membrane composite is not limited to the above. For example, it can also be a method where both ends are connected to the pipe, allowing gas to flow through the inside.

[0142] A catalyst 13 is disposed around the tubular zeolite membrane composite 1. The feed gas introduced through the feed inlet a promotes alcohol formation by contacting the catalyst 13. Furthermore, by permeating the generated alcohol through the zeolite membrane of the zeolite membrane composite 1, alcohols of higher purity can be obtained. Moreover, by selectively permeating the alcohol through the zeolite composite 1, the alcohol concentration in the gas contacting the catalyst 13 is reduced, thereby promoting alcohol formation.

[0143] The other end of pipe 3 is connected to the permeate gas outlet b of the reactor, conveying the alcohol that has passed through the zeolite membrane of the zeolite membrane composite 1 to the permeate gas outlet b. Alternatively, the zeolite membrane composite 1 can be directly connected to the permeate gas outlet b of the reactor without going through pipe 3. In this embodiment, a heat exchanger 101 is provided as a heat recovery device for recovering at least a portion of the reaction heat from the reactor 10. Typically, a heat exchanger can be used as the heat recovery device. Multiple heat recovery devices may also be present. The heat recovery device may be located inside the reactor 10 or adjacent to the reactor 10.

[0144] The alcohol-selective permeable membrane is preferably bonded to a dense component by a bonding material, wherein the bonding material is mainly composed of inorganic oxides and has a linear expansion coefficient of 30 × 10⁻⁶. -7 / K or higher and 90×10 -7 / K or below.

[0145] As inorganic oxides, substances suitable for use as inorganic binders can be appropriately selected. In addition, inorganic glass can also be used. Examples of inorganic oxides include alumina, titanium dioxide, zirconium oxide, silicon dioxide, and magnesium oxide. Examples of inorganic glasses include those containing SiO2, Al2O3, ZnO, P2O5, Bi2O3, BaO, TiO2, TeO2, V2O5, B2O3, and SnO, with lead-free glass being preferred.

[0146] In addition, the main component refers to the component with the highest content (by mass) among all the components constituting the bonding material. It is usually more than 50% by mass of all components, but it can also be more than 70% by mass, more than 80% by mass, or more than 90% by mass.

[0147] The linear expansion coefficient of the bonding materials is typically 30 × 10⁻⁶. -7 / K or higher, preferably 40×10 -7 / K or higher, in addition, it is usually 90×10 -7 / K or less, preferably 80×10 -7 / K or below. If it is within the above range, the adhesion between the alcohol selectively permeable membrane and the dense component is improved, which can impart good sealing (air tightness) and durability.

[0148] The linear expansion rate of the bonding material largely depends on the linear expansion rate of the main component and can be adjusted by mixing in other additives. To achieve a linear expansion rate of 30 × 10⁻⁶... -7 / K or higher and 90×10 -7 For components with a K content below a certain level, alumina, zirconium oxide, silicon dioxide, graphite, P2O5, Bi2O3, SnO, etc., can be used as the main components.

[0149] Commercially available bonding materials can also be used, such as "TB3732" manufactured by ThreeBond Co., Ltd., "Aron Ceramic D" and "Aron Ceramic E" manufactured by Toa Synthetic Co., Ltd., "FP-74", "KP312E", "FP-67", "BNL115BB", "ASF-1094", "ASF-1098", and "ASF-1109" manufactured by AGC Co., Ltd., and "Ceramabond 552" manufactured by Aremco Products Inc.

[0150] A dense component bonded to an alcohol-selective permeable membrane by a bonding material is a component with a degree of density (fineness) that prevents leakage of the gas supplied to the reaction or the gas after the reaction from the component. Examples include caps that seal the ends of tubular components and piping connected to the ends of tubular components. There are no particular limitations on components with such density, and metals are typically used. Examples of metals mentioned herein include stainless steel, ceramics such as alumina and zirconium oxide, and alloys such as Kovar.

[0151] In this embodiment, the linear expansion rate of the dense component is preferably 30 × 10⁻⁶. -7 / K or higher and 200×10 -7 / K or below. By making the linear expansion rate of the dense component within the above range, the difference in linear expansion rate with that of the bonding material can be reduced, ensuring good airtightness and durability.

[0152] Furthermore, the difference in the linear expansion rates between the bonding material and the dense component is preferably 50 × 10⁻⁶. -7 / K or less, preferably 40×10 -7 / K or less, preferably 30×10 -7 / K or less. When the difference in linear expansion rates between the bonding material and the dense component is small, bonding failures caused by material shrinkage during the sintering of the bonding material can be suppressed.

[0153] The alcohol-selective permeable membrane in this embodiment is typically a zeolite membrane, but there are no particular limitations on the type of membrane that can selectively permeate alcohols, and various porous membranes, various MOFs (metal-organic frameworks) and the like can be used. In one embodiment, the zeolite membrane is formed on a porous support component such as alumina and can be used as a zeolite membrane composite.

[0154] The main zeolite constituting the zeolite film is preferably a zeolite with a small-pore structure containing oxygen rings of 12 or fewer or 6 or more members. The 'n' value in the context of zeolites with n-membered oxygen rings refers to the pores containing the largest number of oxygen atoms, formed by oxygen and T elements (elements other than oxygen in the framework) that constitute the zeolite framework. For example, MOR-type zeolites, in the presence of pores with 12-membered and 8-membered oxygen rings, are considered zeolites with 12-membered oxygen rings.

[0155] Examples of zeolites with a small-pore structure containing oxygen rings of twelve or fewer members or more members include those coded by the International Zeolite Association (IZA): AEI, AEL, AFI, AFG, ANA, ATO, BEA, BRE, CAS, CDO, CHA, CON, DDR, DOH, EAB, EPI, ERI, ESV, EUO, FAR, FAU, FER, FRA, HEU, GIS, GIU, GME, GOO, ITE, KFI, LEV, LIO, LOS, LTA, LTL, LTN, MAR, MEP, MER, MEL, MFI, MON, MOR, MSO, MTF, MTN, MTW, MWW, NON, NES, OFF, PAU, PHI, RHO, RTE, RTH, RUT, SGT, OD, STI, STT, TOL, TON, TSC, UFI, VNI, WEI, YUG, etc. Preferably, one of these is selected arbitrarily.

[0156] Furthermore, the zeolite particularly suitable for use in this invention is preferably a zeolite that selectively adsorbs alcohols. More preferably, the zeolite is used for selective adsorption, rather than through a simple molecular sieve (i.e., a sieve based solely on molecular size differences), to allow molecules to pass through. This selective adsorption is used, for example, to allow larger molecules to pass through or to separate substances of similar size. That is, separation is more preferably achieved through selective adsorption on the zeolite surface. Such zeolites exhibit reduced selective adsorption capacity at higher temperatures, thus allowing the effects of this invention to be more significantly realized.

[0157] The ease of alcohol adsorption is strongly influenced by the Si / Al molar ratio in the zeolite. The Si / Al molar ratio in the zeolite is typically 2 or higher, preferably 4 or higher. Furthermore, it is typically 100 or lower, preferably 50 or lower. If the Si / Al molar ratio is low, the stability of the crystal decreases, making synthesis more difficult. Conversely, if the Si / Al molar ratio is high, alcohol adsorption is difficult, and the separation performance cannot be fully utilized. The Si / Al molar ratio in zeolites can be determined using commonly known methods. These include methods such as dissolving the zeolite and measuring it using ICP (inductively coupled plasma atomic emission spectrometry); directly measuring it in its solid state using EDX (energy-dispersive X-ray spectroscopy); and combining it with ion beam sputtering for XPS (X-ray photoelectron spectroscopy). The appropriate method can be selected based on the shape of the film and the material of the support.

[0158] Because zeolites lack flexibility, they are fabricated as supports on certain substrates during film formation. The supports are porous, allowing gas molecules to penetrate them; for example, they have a large number of interconnected, three-dimensional micropores.

[0159] As the material constituting the support, it is preferred to be a chemically stable material that does not react with the untreated gas and has excellent mechanical strength. Specifically, materials such as various alumina, silicon dioxide, silicon dioxide-alumina, mullite, cordierite, zirconium oxide and other oxide ceramics, silicon carbide, carbon, glass, etc. can be used.

[0160] Furthermore, the shape of the support varies depending on the application of the zeolite membrane. In particular, zeolite membranes on cylindrical supports are suitable for batch processes, circulation processes (including recycling processes) due to their high strength in withstanding external pressure.

[0161] In this embodiment, a zeolite film composite with a zeolite film formed on a support can be used. For example, a cylindrical support is prepared, and zeolite microcrystals are first loaded into small holes. Loading methods include impregnation, friction, suction, and immersion. These microcrystals act as nuclei during the growth of the crystals constituting the zeolite film, and are also called seed crystals. The zeolite growth can be performed using hydrothermal synthesis, similar to zeolite synthesis.

[0162] The thickness of the zeolite membrane in the zeolite membrane composite is not particularly limited, but is typically 0.1 μm or more, preferably 0.5 μm or more, and also typically 50 μm or less, preferably 20 μm or less. By making the membrane thickness above the specified value, sufficient compactness can be obtained, maintaining high membrane selectivity. Furthermore, by making the membrane thickness below the specified value, sufficient gas permeation can be obtained.

[0163] In the catalyst bed within the reactor, a heat recovery device and an alcohol-selective permeation membrane can also be installed throughout the entire region along the flow direction of the feed gas from upstream to downstream. Alternatively, only a heat recovery device can be installed in the upstream section, while an alcohol-selective permeation membrane and a heat recovery device can be installed in the downstream section. The reactor can have one reaction chamber or be divided into two or more. When divided into two or more, heat recovery devices and alcohol-selective permeation membranes can be installed in all reaction chambers. Alternatively, alcohol-selective permeation membranes can be installed only in the downstream reaction chambers instead of the upstream ones. When the reaction chambers are divided into two or more, heat recovery devices can be omitted in the reaction chambers that generate less heat.

[0164] As a method of using the heat recovered in the heat recovery unit as a heat source for the process, the uncondensed feedstock can also be recovered from the outlet gas of the non-permeable side and / or the permeable side and then returned to the upstream of the reactor.

[0165] The area of ​​the alcohol-selective permeable membrane in the reactor is set using the ratio of membrane area (A) per unit catalyst volume (V) to V (m²). 2 / m 3 ) is used to represent. Catalyst volume refers to the packed volume (m³) of catalyst in the reactor. 3 The catalyst weight (kg) is divided by the bulk density (kg / m³). 3 The value obtained is ).

[0166] Membrane area (m²) 2 The area of ​​the alcohol-selective permeable membrane installed within the reactor is the macroscopic apparent area. For example, if it is a four-sided flat plate type alcohol-selective permeable membrane, it is approximated as a cuboid, and the area (length × width) of the face containing the alcohol-selective permeable membrane within the approximate cuboid is taken as the membrane area. Furthermore, if it is a cylindrical alcohol-selective permeable membrane, it is approximated as a cylinder, and the lateral surface area (diameter × pi × height) of the cylinder is taken as the membrane area.

[0167] When the reactor is divided into multiple units, the catalyst volume and membrane area are the sum of the values ​​of all reactors. The membrane area per unit catalyst volume, A / V, is typically 5 or more, preferably 10 or more, and also typically 150 or less, preferably 120 or less. If the membrane area per unit catalyst volume, A / V, is too small, the conversion improvement effect brought about by the selective permeation of alcohol through the membrane cannot be fully obtained; if it is too large, the equipment cost increases.

[0168] The separation selectivity of alcohol-selective permeation membranes is expressed as the ratio of the permeation coefficient of the target analyte to that of the non-target analyte. The permeation coefficient refers to the area per unit membrane cell (m²). 2 The parameters are: unit pressure difference (Pa), unit time (s), and permeate mass (mol). Additionally, the pressure difference (Pa) mentioned here refers to the difference between the partial pressure of a substance on the non-permeable side of the membrane and the partial pressure on the permeable side.

[0169] The transmittance ratio in this specification is the value obtained by dividing the transmittance of the separated object measured at the same process temperature by the transmittance of the non-separated object measured at the same process temperature. The alcohol to hydrogen permeability ratio (alcohol / hydrogen permeability ratio) is typically 10 or higher, preferably 20 or higher, and more preferably 50 or higher. If the alcohol to hydrogen permeability ratio is too low, the feed loss on the permeation side increases, the amount of recovered gas increases, and energy consumption increases.

[0170] (Explanation of manufacturing method) Another embodiment of the present invention is an alcohol manufacturing method, comprising a synthesis step of reacting a raw material containing at least hydrogen and carbon monoxide and / or carbon dioxide in the presence of a catalyst to synthesize an alcohol, the alcohol manufacturing method comprising: a separation and recovery step of separating and recovering the obtained alcohol in a reactor using an alcohol selective permeation membrane having zeolite, and a heat recovery step of recovering at least a portion of the heat of reaction generated in the synthesis step from the reactor, wherein the separation and recovery step is performed simultaneously with the heat recovery step.

[0171] In this embodiment, the raw materials, catalyst, alcohol-selective permeable membrane, reactor, etc., can be the substances described above. In this embodiment, in the reactor, in the presence of a catalyst, a raw material gas containing at least hydrogen and carbon monoxide and / or carbon dioxide is reacted to obtain an alcohol. The reaction conditions are not particularly limited, but the reaction temperature is typically 200°C or higher, preferably 210°C or higher, more preferably 220°C or higher, and typically 300°C or lower, preferably 290°C or lower, more preferably 270°C or lower. These upper and lower limits can be combined arbitrarily. Furthermore, the reaction temperature refers to the temperature of the gas inside the reactor. By setting the reaction temperature above the aforementioned lower limit, the reaction rate is increased, and the productivity is improved. By setting the reaction temperature below the aforementioned upper limit, the chemical equilibrium of the reaction is favorable for obtaining an alcohol, thus improving the conversion rate even if the membrane performance is somewhat reduced. Furthermore, the permissible range of heat resistance required for the bonding material is also increased.

[0172] The alcohol obtained through the above reaction is recovered from the permeate gas outlet of the reactor via a separation and recovery step, passing through an alcohol-selective permeation membrane within the reactor. Furthermore, a heat recovery step is performed simultaneously with the separation and recovery step to recover at least a portion of the reaction heat generated during alcohol synthesis from the reactor. It may also include a step of supplying at least a portion of the heat of reaction recovered in this heat recovery step to heat one or more feedstocks selected from hydrogen, carbon monoxide, and carbon dioxide before they are introduced into the reactor. Additionally, the recovered heat of reaction may be used for other purposes.

[0173] The pressure inside the reactor when the generated alcohol permeates through the alcohol-selective permeation membrane, i.e., the pressure (gauge pressure) on the gas supply side of the alcohol-selective permeation membrane in the reactor, is preferably 1 MPaG or more, more preferably 2 MPaG or more, more preferably 8 MPaG or less, and more preferably 5 MPaG or less. By maintaining the pressure within a suitable range, the limitation of reaction equilibrium can be reduced, and the reaction rate can be increased, making it easier to achieve higher productivity. In addition, the increase in reactor manufacturing costs and feed gas pressurization costs caused by excessive pressure can be suppressed.

[0174] Furthermore, within the reaction vessel, the alcohol partial pressure (absolute pressure) on the gas supply side of the alcohol selectively permeating membrane is preferably 0.1 MPaA or more, more preferably 0.2 MPaA or more, more preferably 6 MPaA or less, and more preferably 5 MPaA or less. By maintaining the alcohol partial pressure within this range, a sufficient amount of alcohol permeates through the membrane, maximizing the membrane's effectiveness. On the other hand, if it is within this range, the durability and sealing required for the joints will not be unnecessarily increased, allowing for simple and large-scale jointing.

[0175] The gauge pressure within the reactor described above can be measured using a pressure gauge located within the reactor. Furthermore, the absolute pressure of the alcohol within the reactor varies from upstream to downstream; here, the absolute pressure of the alcohol within the reactor is taken as the analytical result of the reactor outlet gas composition obtained from gas chromatography and the value calculated using gauge pressure. Example

[0176] The present invention will be described in more detail below based on embodiments, but the present invention is not limited to the following embodiments without departing from its spirit. Furthermore, various measurements and evaluations in the embodiments are performed as follows.

[0177] <Coefficient of thermal expansion of inorganic glass and dense components> The coefficient of thermal expansion (coefficient of linear expansion) of inorganic glass frit and dense components at 30–250°C is determined by preparing cylindrical test pieces with a diameter of approximately 5 mm and a length of approximately 10–20 mm from the sample. The expansion of the test pieces within the above temperature range is measured using a differential thermal dilatometer (Rigaku Corporation, TMA8310), and the average coefficient of linear expansion is calculated. Furthermore, this embodiment uses catalog values ​​or manufacturer data values.

[0178] <Softening point of inorganic glass> The softening point was determined using a differential thermal analysis (DTA) apparatus (Rigaku Corporation TG8120). The glass frit, pulverized in a mortar, was heated at a rate of 10 °C / min, and the second inflection point of the obtained DTA curve was taken as the softening point. In addition, the values ​​recorded in this embodiment are product catalog values ​​or manufacturer data values.

[0179] <Air Transmission Measurement> Under atmospheric pressure, the end of the connector (the end without the cap) was connected to a 5 kPa vacuum line while maintaining an airtight seal. A mass flow meter positioned between the vacuum line and the connector was used to measure the airflow rate through the zeolite membrane composite. sccm represents cc / min converted to 0°C and 1 atm. A Brooks Instruments GF40 mass flow meter (maximum flow rate 20 sccm) was used.

[0180] <Durability Testing> The composite obtained in the examples and comparative examples was added to an 80ml autoclave made of 316 stainless steel. 5ml of methanol and 5ml of demineralized water were then added, and the autoclave was sealed and placed in an electric furnace. The furnace was heated to 280°C for 1 hour. At this point, the pressure inside the autoclave was 3.5MPa. Heating was stopped after 48 hours at 280°C, and the autoclave was removed from the furnace and allowed to cool naturally. After cooling for at least 2 hours, the autoclave was opened and the composite was removed. It was then dried at 120°C under normal pressure for 4 hours before the air permeability was measured.

[0181] First, specific examples of the first and second embodiments will be explained. <Example A1> (Preparation of a composite of zeolite and alumina porous support) A cylindrical porous alumina support (outer diameter 12 mm, inner diameter 9 mm, total length 40 mm) pre-seeded with crystals was vertically immersed in a Teflon (registered trademark) inner cylinder containing an aqueous reaction mixture with a molar ratio of SiO2:Na2O:Al2O3:H2O = 100:27.8:0.021:4000. The mixture was then placed in a sealed autoclave and subjected to hydrothermal synthesis at 180°C for 12 hours. After the specified time, the mixture was allowed to cool to room temperature. The porous support-zeolite composite was then removed from the reaction mixture, washed, and dried at 120°C for at least 4 hours to obtain an MFI-type zeolite and alumina porous support composite.

[0182] (Fabrication of the joint) The cap is made of Kovar alloy (coefficient of thermal expansion 52×10). -7 The recess filling of the lead-free inorganic glass "FP-74" (coefficient of thermal expansion 63×10⁻⁶) manufactured by AGC Corporation is used as a lead-free inorganic glass. The glass filler has a diameter of 14.0 mm, an outer diameter of 12.2 mm, and a height of 4 mm. -7A composite of the above-mentioned MFI-type zeolite and alumina porous support was placed on top of a 0.3g sample containing K (softening point 355℃, SnO content 42%). Then, with a 560g weight placed on top of the composite, the mixture was placed in a muffle furnace and heated to 480℃ over 100 minutes, maintaining this temperature for 30 minutes. Heating was then stopped, and the mixture was allowed to cool naturally to obtain the bonded body.

[0183] The resulting joint was subjected to air permeability measurement and durability testing. The results showed that the air permeability of the joint before the durability test was less than 0.1 sccm. Furthermore, the air permeability of the joint after the durability test was also less than 0.1 sccm, showing no change before and after the test, indicating good durability.

[0184] <Example A2> As an inorganic glass, it uses glass material "KP312E" (thermal expansion coefficient 71×10⁻⁶) manufactured by AGC Corporation. -7 / K, softening point 344℃, SnO content 52%), and the calcination temperature in the muffle furnace is 430℃. Otherwise, the joint is obtained by the same method as in Example A1.

[0185] The resulting joint was subjected to air permeability measurement and durability testing. The results showed that the air permeability of the joint before the durability test was less than 0.1 sccm. Furthermore, the air permeability of the joint after the durability test was also less than 0.1 sccm, showing no change before and after the test, indicating good durability.

[0186] <Example A3> As an inorganic glass, it uses glass material "FP-67" (coefficient of thermal expansion 79×10⁻⁶) manufactured by AGC Corporation. -7 / K, softening point 357°C, SnO content 50%), except that the joint was obtained by the same method as in Example A1.

[0187] The air permeability of the resulting joint was measured. The results showed that the air permeability of the joint was less than 0.1 sccm.

[0188] <Example A4> As an inorganic glass, it uses glass material "BNL115BB" (coefficient of thermal expansion 74×10⁻⁶) manufactured by AGC Corporation. -7 / K, softening point 397℃, B2O3 content 5.0%), and calcined in a muffle furnace at 500℃, otherwise the joint was obtained by the same method as in Example A1.

[0189] The resulting joint was subjected to air permeability measurement and durability testing. The results showed that the air permeability of the joint before the durability test was 0.4 sccm. Furthermore, the air permeability of the joint after the durability test was also 0.4 sccm, with no change in air tightness.

[0190] <Example A5> The joint of Example A4 was subjected to a sealing treatment. Specifically, in the joint between the MFI-type zeolite and alumina porous support composite and the cap, a methyl silicate oligomer "MKC Silicate (registered trademark) MS-56" manufactured by Mitsubishi Chemical Corporation was coated while the interior was depressurized. After being left at room temperature for 1 hour, the sealing treatment was completed by heat treatment at 250°C for 30 minutes.

[0191] The resulting joint was subjected to air permeability measurement and durability testing. The results showed that the air permeability of the joint before the durability test became below 0.1 sccm, and the airtightness was improved by sealing treatment. In addition, it can be seen that the air permeability of the joint after the durability test was below 0.1 sccm, with no change before and after the test, demonstrating good durability.

[0192] <Example A6> As an inorganic glass, it uses glass material "BF-0606" manufactured by Nippon Electric Glass Co., Ltd. (coefficient of thermal expansion 72×10). -7 / K, softening point 450℃, B2O3 content 6.4%), and calcination temperature in muffle furnace is 485℃. Otherwise, the joint is obtained by the same method as in Example A1.

[0193] The resulting joint was subjected to air permeability measurement and durability testing. The results showed that the air permeability of the joint before the durability test was 0.2 sccm. Furthermore, it was found that the air permeability of the joint after the durability test was also 0.2 sccm, with no change in air tightness.

[0194] <Example A7> As an inorganic glass, it uses glass material "BF-0901" manufactured by Nippon Electric Glass Co., Ltd. (coefficient of thermal expansion 48×10). -7 / K, softening point 528°C, B2O3 content 9.7%, and the calcination temperature in the muffle furnace is 560°C. Otherwise, the joint is obtained by the same method as in Example A1.

[0195] The resulting joint was subjected to air permeability measurement and durability testing. The results showed that the air permeability of the joint before the durability test was less than 0.1 sccm. Furthermore, the air permeability of the joint after the durability test was also less than 0.1 sccm, showing no change before and after the test, indicating good durability.

[0196] <Example A8> As an inorganic glass, it uses glass material "ASF-1094" (coefficient of thermal expansion 79×10⁻⁶) manufactured by AGC Corporation. -7 / K, softening point 533℃, B2O3 content 15%), and the calcination temperature in the muffle furnace is 550℃. Otherwise, the joint is obtained by the same method as in Example A1.

[0197] The resulting joint was subjected to air permeability measurement and durability testing. The results showed that the air permeability of the joint before the durability test was 0.3 sccm. Furthermore, it was found that the air permeability of the joint after the durability test was also 0.3 sccm, with no change in air tightness.

[0198] <Example A9> As an inorganic glass, it uses glass material "ASF-1098" manufactured by AGC Corporation (coefficient of thermal expansion 54×10⁻⁶). -7 / K, softening point 515℃, B2O3 content 16%), and the calcination temperature in the muffle furnace is 560℃. Otherwise, the joint is obtained by the same method as in Example A1.

[0199] The air permeability of the resulting joint was measured. The results showed that the air permeability of the joint was less than 0.7 sccm.

[0200] <Example A10> As an inorganic glass, it uses glass material "ASF-1109" (coefficient of thermal expansion 65×10⁻⁶) manufactured by AGC Corporation. -7 / K, softening point 545℃, B2O3 content 19%), and the calcination temperature in the muffle furnace is 560℃. Otherwise, the joint is obtained by the same method as in Example A1.

[0201] The air permeability of the resulting joint was measured. The results showed that the air permeability of the joint was less than 1.2 sccm.

[0202] <Comparative Example A1> As an inorganic glass, it uses glass material "SK-231-300" manufactured by AGC Corporation (coefficient of thermal expansion 84×10⁻⁶). -7 / K, softening point 559℃, B2O3 content 13%), and the calcination temperature in the muffle furnace is 580℃. Otherwise, the joint is obtained by the same method as in Example A1.

[0203] The air permeability of the resulting joint was measured. The results showed that the air permeability of the joint was less than 5.5 sccm.

[0204] <Comparative Example A2> As an inorganic glass, it uses glass material "KF9173" (thermal expansion coefficient 98×10⁻⁶) manufactured by AGC Corporation. -7 / K, softening point 462℃, B2O3 content 11%), and the calcination temperature in the muffle furnace is 520℃. Otherwise, the joint is obtained by the same method as in Example A1.

[0205] The resulting joint was subjected to air permeability measurement and durability testing. The results showed that the air permeability of the joint before the durability test was 7.3 sccm. Furthermore, the air permeability of the joint after the durability test was above 20 sccm (outside the measurement range), indicating a deterioration in airtightness.

[0206] [Table 1] Table 1

[0207] Below, a specific example of a third embodiment using an inorganic adhesive as a bonding material is shown.

[0208] (Example B1) (Preparation of a composite of zeolite and alumina porous support) A porous alumina support (outer diameter 12 mm, inner diameter 9 mm, total length 40 mm) pre-seeded with crystals was vertically immersed in a Teflon (registered trademark) inner cylinder containing an aqueous reaction mixture with a composition of 100SiO2:27.8Na2O:0.021Al2O3:4000H2O. The mixture was then placed in a sealed autoclave and subjected to hydrothermal synthesis at 180°C for 12 hours. After the specified time, the mixture was allowed to cool to room temperature. The porous support-zeolite composite was then removed from the reaction mixture, washed, and dried at 120°C for at least 4 hours to obtain a composite of MFI-type zeolite and porous alumina support.

[0209] (Fabrication of the joint) The cap is made of Kovar alloy (outer diameter 14.0 mm, inner diameter 12.2 mm, height 4 mm, coefficient of thermal expansion 52 × 10⁻⁶). 7The recess of / K is filled with “TB3732” (alumina-based, with a thermal expansion coefficient of 80×10⁻⁶ after curing) manufactured by ThreeBond Co., Ltd. as an inorganic adhesive. 7 A composite of the above-mentioned MFI-type zeolite and alumina porous support was placed on top of a 0.6g metal alkoxide (K). A 560g weight was then placed on top of the composite to apply a load, and the mixture was left at room temperature for 1 hour. Next, it was heated to 100°C for 30 minutes and then allowed to cool naturally to obtain the bonded body.

[0210] (Example B2) The joint of Example 1 was subjected to a sealing treatment. Specifically, in the joint between the MFI-type zeolite and alumina porous support composite and the cap, a methyl silicate oligomer "MKC Silicate (registered trademark) MS-56" manufactured by Mitsubishi Chemical Corporation was coated while the interior was depressurized. After being left at room temperature for 1 hour, it was heat-treated at 250°C for 30 minutes to form a sealing film. The air permeability was measured to be less than 0.1 sccm, and the sealing performance was improved by the sealing film.

[0211] (Example B3) As an inorganic binder filler, it is used in "Aron Ceramic D" (alumina-based, with a coefficient of thermal expansion of 80×10⁻⁶ after curing) manufactured by Toa Synthetic Co., Ltd. -7 A composite of the above-mentioned MFI-type zeolite and alumina porous support was placed on top of a 0.6g (K, free of metal alkoxides) substrate. A 560g weight was then placed on top of the composite to apply a load, and the mixture was left at room temperature for 20 hours. It was then heated to 90°C for 1 hour, followed by a further heating to 150°C for 1 hour, and then allowed to cool naturally to obtain the bond. The air permeability was measured to be 14 sccm.

[0212] (Example B4) Using the joint from Example B3, except that a sealing treatment was performed in the same manner as in Example 2, a joint was obtained. The air permeability was measured to be less than 0.1 sccm, indicating that the sealing performance was improved by the sealing treatment.

[0213] (Example B5) As an inorganic binder, "Aron Ceramic E" (zirconia-silica based, with a coefficient of thermal expansion of 40 × 10⁻⁶ after curing) manufactured by Toa Synthetic Co., Ltd. is used. -7 / K, free of metal alkoxides), except that the conjugate was obtained by the same method as in Example B3. The air permeability was measured to be 18 sccm.

[0214] (Example B6) Using the joint from Example B5, except that a sealing process was performed in the same manner as in Example B2, a joint was obtained. The air permeability was measured to be less than 0.1 sccm, and the sealing performance was improved by the sealing film.

[0215] (Example B7) Instead of the methyl silicate oligomer "MKC Silicate (registered trademark) MS-56" manufactured by Mitsubishi Chemical Corporation, "Permeate HS-90" manufactured by D&D CORPORATION was used. Except for this, the sealing treatment was performed using the same method as in Example 2 to obtain the bond. The air permeability was measured to be less than 0.1 sccm, indicating improved sealing performance through the sealing film.

[0216] (Comparative Example B1) As an inorganic binder, it uses "Aron Ceramic C" (silica-based, with a coefficient of thermal expansion of 130 × 10⁻⁶ after curing) manufactured by Toa Synthetic Co., Ltd. -7 (K, free of metal alkoxides), except that the conjugate was obtained using the same method as in Example B3. The air permeability was measured to be 103 sccm. The results of Examples B1-7 and Comparative Example B1 are shown in Table 2.

[0217] [Table 2] Table 2

[0218] (Example B8) (Durability test) The bond from Example B1 was added to an 80ml autoclave made of 316 stainless steel. Then, 5ml of methanol and 5ml of demineralized water were added, and the autoclave was sealed and placed in an electric furnace under atmospheric pressure. The furnace was heated to 280°C for 1 hour. Heating was stopped after 48 hours at 280°C (pressure 3.2 MPaG). The autoclave was then removed from the furnace and allowed to cool naturally. After cooling for at least 2 hours, the autoclave was opened and the bond was removed. It was then dried at 120°C under normal pressure for 4 hours, and the air permeability was measured to be 0.3 sccm, showing no change before and after the test, indicating good durability.

[0219] (Example B9) The joint of Example B2 was used, except that the durability test was performed in the same manner as in Example B8. The air permeability was less than 0.1 sccm.

[0220] (Example B10) The bonding assembly of Example B7 was used, except that the durability test was performed in the same manner as in Example B8. The air permeability was 0.2 sccm.

[0221] (Comparative Example B2) The bonding assembly of Comparative Example B1 was used, except that the durability test was performed in the same manner as in Example B8. The air permeability was 300 sccm or more (exceeding the measurement range).

[0222] (Comparative Example B3) Using "TB1208B" (silicone-based, metal alkoxide-free) manufactured by ThreeBond Co., Ltd. (which is not an inorganic binder) as the binder, the joint was obtained by heating at 120°C for 1 hour instead of heating at 100°C for 30 minutes, except that the method was the same as in Example B1. The air permeability was measured to be less than 0.1 sccm. Then, using this joint, a durability test was performed in the same manner as in Example B7. The joint fractured, and the composite of the MFI-type zeolite and the porous alumina support split between the cap and the joint. The results of Examples B8-10 and Comparative Examples B2-3 are shown in Table 3.

[0223] [Table 3] Table 3

[0224] Next, a specific example of the fourth embodiment of the present invention will be shown. <Example C1> A porous alumina support pre-seeded with crystals was vertically immersed in a Teflon (registered trademark) inner cylinder containing an aqueous reaction mixture with a composition of 100SiO2:27.8Na2O:0.021Al2O3:4000H2O. The mixture was then placed in a sealed autoclave and subjected to hydrothermal synthesis at 180°C for 12 hours. After the specified time, the mixture was allowed to cool to room temperature. The porous support-zeolite composite was then removed from the reaction mixture, washed, and dried at 120°C for at least 4 hours to obtain an MFI-type zeolite and porous alumina support composite (hereinafter referred to as the membrane composite). The membrane composite was then cut and used as needed.

[0225] The glass material "BNL115BB" manufactured by AGC Corporation (with a linear expansion rate of 74×10⁻⁶ after firing) was used. 7 / K)" will be used to make the cap of Kovar alloy (linear expansion coefficient 52×10) 7 / K), Kovar alloy connecting pipe (linear expansion coefficient 52×10), 7The membrane composite ( / K) was calcined in a muffle furnace at 500°C for 30 minutes, and then the membrane composite, cap, and connecting tube were joined. The effective membrane length of the joined membrane composite was 34 mm.

[0226] <Methanol Manufacturing> Methanol production was carried out using a fixed-bed reactor (120 mL internal volume) made of 316L stainless steel. A Kovar alloy connecting pipe, which is connected to the membrane complex, was attached to the reactor using a Swagelok® connector. The membrane complex was surrounded by 75 g of Cu-Zn composite oxide catalyst F07J (containing 49 wt% CuO, 45 wt% ZnO, and 5.6 wt% Al2O3) manufactured by Nippon Kaisha Co., Ltd., and the reactor was sealed. Before the reaction, H2 diluted with N2 (H2 / N2 = 25 / 75, molar concentration) was circulated at a rate of 100 mL / min in the reactor to reduce the catalyst for 6 hours at 300 °C and atmospheric pressure. After the catalyst reduction was complete, the reactor was cooled, and the flowing gas was switched to synthesis gas (feed gas: H2 / CO = 66.9 / 33.1, molar ratio) at 332 mL / min. A membrane separation reaction was carried out at a reactor temperature of 250°C and an internal pressure of 3 MPaG. The methanol partial pressure inside the reactor was 0.55 MPaA.

[0227] Both membrane-permeable and membrane-permeable components of the gaseous products were analyzed using N2 as an internal standard in an online gas chromatograph. Once the analytical results were stable, CO was calculated using Equation 4 below. x Conversion rate. Formula 4: CO x Conversion rate = 1 - (CO flow rate at non-permeable gas outlet + CO2 flow rate at non-permeable gas outlet + CO flow rate at permeable gas outlet + CO2 flow rate at permeable gas outlet) / (CO flow rate at feed inlet + CO2 flow rate at feed inlet) Furthermore, based on the equilibrium of the methanol synthesis reaction shown in Equations 1 and 2, the equilibrium CO2 can be calculated. x Conversion rate, as an indicator of the rate of increase in conversion rate relative to the equilibrium conversion rate, is used to calculate CO. x Conversion rate / Balanced CO x Conversion rate. Equation 1: 3H2 + CO2 ⇌ CH3OH + H2O Equation 2: 2H2 + CO ←→ CH3OH

[0228] <Example C2> The reactor pressure was set to 1.5 MPaG, and otherwise carried out in the same manner as in Example C1, resulting in Example C2. Additionally, the methanol partial pressure inside the reactor was 0.33 MPaA.

[0229] <Example C3> The reactor temperature was set to 230°C, and the feed gas flow rate was 83 mL / min. Otherwise, the process was the same as in Example C1, resulting in Example C3. The methanol partial pressure obtained in the reactor was 0.87 MPaA.

[0230] <Example C4> Using other batches of film composites synthesized under the same conditions as in Example C1, glass frit "FP-74" manufactured by AGC Corporation (with a linear expansion coefficient of 63 × 10⁻⁶ after calcination) was used. 7 / K)” is used for bonding with the Kovar alloy cap and connecting tube, and the calcination temperature is changed to 480°C. Otherwise, the bonding of the membrane composite with the cap and connecting tube is performed in the same manner as in Example C1. The effective membrane length of the bonded membrane composite is 38 mm. The catalyst amount was 75g, and the feed gas was a synthesis gas containing CO2 at a flow rate of 147mL / min (H2 / CO / CO2 = 69.5 / 23.2 / 7.3 molar ratio). Methanol was produced in the same manner as in Example C1, as Example C4. The methanol partial pressure in the reactor was 0.71MPaA.

[0231] <Example C5> The composition of the circulating gas was H2 / CO2 = 75 / 25 (molar ratio), and the flow rate was 131 mL / min. Otherwise, the process was the same as in Example C4, resulting in Example C5. Additionally, the methanol partial pressure in the reactor was 0.22 MPaA.

[0232] <Example C6> Using other batches of membrane composites synthesized under the same conditions as in Example C1, the inorganic binder "Ceramabond 552" manufactured by Aremco Products Inc. (with a linear expansion rate of 77 × 10⁻⁶ after calcination) was applied. 7 The " / K)" is used for bonding with Kovar alloy caps and connecting tubes. After calcining at 93°C for 2 hours, it is further calcined at 260°C for 2 hours to complete the bonding. The effective membrane length of the bonded membrane composite is 28 mm. The catalyst amount was 30g, and the flow rate of the feed gas was 321mL / min. Methanol was produced in the same manner as in Example C1, as Example C6. The methanol partial pressure in the reactor was 0.32MPaA.

[0233] [Table 4] Table 4

[0234] In Table 4, the CO values ​​of each embodiment C are shown. x Conversion rate / Balanced CO x The conversion rates are all greater than 1, indicating that the methanol synthesis reaction has proceeded to equilibrium. That is, through this invention, methanol can be efficiently produced with a conversion rate greater than the equilibrium conversion rate.

[0235] <Reference Example C1> Durability tests were conducted on O-rings, commonly used as bonding materials in mechanical seals. Kalrez® 6375, 7075, 0090, and 7090 O-rings were used. The durability test was conducted by sealing 5 mL of methanol, 5 mL of water, and the bonding material in a 70 mL high-pressure vessel made of 316 stainless steel or Hastelloy nickel alloy. After replacing the contents of the vessel with nitrogen (N2), the vessel was heated at 250°C for a specified time. Following the tests, the durability of Kalrez(R) was evaluated using a hardness test (JIS K6253-2:2012). Since Kalrez(R) 6375 and 0090 showed a decrease in hardness over time, they were determined to be unsuitable for use under high temperature, high pressure, and in the presence of methanol vapor. Furthermore, Kalrez(R) 7075 and 7090 exhibited significant deformation during the tests, making hardness testing impossible; therefore, they were also deemed unsuitable for use under high temperature, high pressure, and in the presence of methanol vapor.

[0236] <Reference example C2> Durability tests were conducted on graphite gaskets, which are commonly used as bonding materials in mechanical seals. The graphite gaskets used were TOMBO No. 2200-P, 2250 manufactured by NICHIAS CORPORATION. The durability tests were conducted using the same method as in Reference Example C1. After the test, it was found that the graphite was peeling off from each other, so it was determined that it could not be used under high temperature and high pressure, in the presence of methanol vapor. <Reference Example C3> Durability tests were conducted on Aremco-Bond 631, a high-vacuum epoxy adhesive used as a bonding material. The tests were performed using a sample of alumina plate bonded with Aremco-Bond 631 and porous alumina, following the same method as in Reference Example C1. After the test, it was determined that the bonded alumina plate separated from the porous alumina, therefore it could not be used under high temperature and high pressure, or in the presence of methanol vapor.

[0237] As stated above, since it can be determined that the bonding method shown in the reference example cannot be used under high temperature and high pressure, and in the presence of methanol vapor, it cannot be used to manufacture methanol.

[0238] The fifth embodiment of the present invention will be described in more detail below, but it is self-evident that the scope of the present invention is not limited to the embodiments shown in the following examples.

[0239] <Example D1> Taking the process of synthesizing methanol from a mixture of hydrogen, carbon monoxide, and carbon dioxide as an example, the implementation... Figure 8 The process simulation shown is for the schematic flow diagram. The simulation uses ASPEN Plus V8.4 and ASPENCustom Modeler V8.4 from Aspen Technology, Inc. The process conditions are assumed as follows. Raw material gas temperature: 40℃ Temperature of the raw gas after preheating: 230℃ Reaction temperature: 250℃ Pressure (non-permeable side): 5 MPaG Pressure (through side): 0.1 MPaG The feed gas is a mixture of H2 and CO2 at a flow rate of 100 kmol / hr. Its composition, when combined with the recovered gas, satisfies the stoichiometric ratio for methanol synthesis: "H2 flow rate = 2 × CO flow rate + 3 × CO2 flow rate". Catalyst quantity: 2000 kg Film area per unit catalyst volume: 37.5 m² 2 / m 3

[0240] Assuming the reactions that can occur within the reactor, we assume the following three equilibrium reactions. 3H₂ + CO₂ → CH₃OH + H₂O …… Equation 1 2H₂ + CO → CH₃OH …… Equation 2 CO2 + H2 → CO + H2O …… Equation 3 The respective reaction rate formulas refer to Non-Patent Literature 1 and 2 and use the following formulas.

[0241] [Number 1] Equation 1: Reaction rate formula Equation 2: Reaction rate formula Equation 3: Reaction rate formula k3 (mol / kg s bar) = 1.22 × 10 10 exp(-94765 / RT),k4=3453.38,k5(bar 0.5= 0.499exp(17197 / RT), k6(bar -1 ) = 6.62 × 10 -11 exp(124119 / RT), K3=10 (2073 / T-2.029)

[0242] The performance values ​​of the separation membrane are used below. Transmission coefficients of MeOH and H2O: 1.0 × 10⁻⁶ -6 mol / m 2 s Pa Transmission coefficient of components other than MeOH and H2O: 1.0 × 10⁻⁶ -8 mol / m 2 s Pa

[0243] The conversion rate and recovered heat for a single pass were determined through process simulation. The conversion rate was calculated using the mol flow rates of CO and CO2 at the reactor inlet and outlet (the sum of the non-permeable and permeable sides) according to Equation 5. The recovered heat was taken as the amount of heat removed necessary to maintain the reactor temperature at 250°C. Conversion rate (%) = 100 - (outlet CO mol flow rate + outlet CO 2 mol flow rate) / (inlet CO mol flow rate + inlet CO 2 mol flow rate) × 100 ... Equation 5

[0244] <Example D2> like Figure 10 As shown, the process involves only reaction and heat recovery in the first reactor, and simultaneous reaction, membrane separation, and heat recovery in the second reactor. Apart from this, the conversion rate and recovered heat were determined through the same simulation as in Example D1. Furthermore, the total amount of catalyst was the same as in Example 1, and it was evenly distributed between the two reactors. Additionally, the membrane area was based on the total catalyst volume and was the same as in Example D1.

[0245] <Comparative Example D1> like Figure 11 As shown, only the reaction and heat recovery occur within the reactor (the membrane area per unit catalyst volume is 0 m²). 2 / m 3 The process involves no airflow through the permeable side. In addition, the conversion rate and recovered heat are determined through the same simulation as in Example D1.

[0246] <Comparative Example D2> like Figure 12As shown, the process involves reaction and heat recovery in the first reactor, membrane separation only in the second reactor, and reaction and heat recovery only in the third reactor. Except for this, the conversion rate and recovered heat are determined through the same simulation as in Example D1. Furthermore, the total amount of catalyst is the same as in Example D1, and it is evenly distributed in the first and third reactors. Additionally, the membrane area is set in the second reactor with the same area as in Example D1, based on the total catalyst volume.

[0247] As shown in Table D1, the results show that in a process that simultaneously performs reaction, membrane separation, and heat recovery, the conversion rate is improved and the amount of heat that can be recovered is also greater.

[0248] [Table 5] Table D1

[0249] <Reference Example D1> Figure 8 In this embodiment, no heat recovery is performed. Otherwise, the process is assumed to be the same as in the example, and the reactor temperature is estimated by assuming that the heat of reaction is used to raise the temperature of the catalyst layer. However, even after exceeding the heat resistance temperature of the membrane, the increase in reactor temperature did not stop.

[0250] <Example D3> The pressure (non-permeable side) was set to 3 MPaG, the feed gas composition was H2 / CO = 2 / 1, and the feed gas flow rate was 75 kmol / hr. Otherwise, the conversion rate was determined by simulation in the same manner as in Example D1.

[0251] <Example D4> The permeability coefficient of components other than MeOH and H2O is 5.0 × 10⁻⁶. -8 mol / m 2 In addition, the conversion rate was determined by the same simulation as in Example D3.

[0252] <Example D5> The permeability coefficient of components other than MeOH and H2O is 1.0 × 10⁻⁶. -7 mol / m 2 In addition, the conversion rate was determined by the same simulation as in Example D3.

[0253] <Comparative Example D3> Assuming a process without using a separation membrane, the membrane area per unit catalyst volume is 0 m². 2 / m 3 In addition, the conversion rate was determined through the same simulation as in Example D3.

[0254] As shown in Table D2, the results are independent of the ratio of the permeation coefficient, and the conversion rate is higher when using a separation membrane compared to when no separation membrane is used.

[0255] [Table 6] Table D2

[0256] <Example D6> Implementation Figure 13 The schematic flow diagram shown is a simulation of a process excluding recycling. The process conditions are assumed as follows. Reaction temperature: 250℃ Pressure (non-permeable side): 5 MPaG Pressure (through side): 0.1 MPaG Raw material gas: H2 / CO2 = 3 / 1, flow rate 100 kmol / hr Catalyst quantity: 2000 kg Film area per unit catalyst volume: 20m² 2 / m 3 The assumed reaction and reaction rate formulas, and the performance of the separation membrane were used with the same values ​​as in Example D1, and the conversion rate was determined by simulation.

[0257] <Example D7> The reaction temperature was set to 210°C, and the conversion rate was determined by the same simulation as in Example D6.

[0258] <Example D8> The reaction temperature was set to 230°C, and the conversion rate was determined by the same simulation as in Example D6.

[0259] <Example D9> The reaction temperature was set to 270°C, and the conversion rate was determined by the same simulation as in Example D6.

[0260] <Example D10> The reaction temperature was set to 290°C, and the conversion rate was determined by the same simulation as in Example D6.

[0261] <Comparative Example D4> Assuming a process without using a separation membrane, the membrane area per unit catalyst volume is 0 m². 2 / m 3 In addition, the conversion rate was determined through the same simulation as in Example D6.

[0262] <Comparative Example D5> Assuming a process without using a separation membrane, the membrane area per unit catalyst volume is 0 m².2 / m 3 In addition, the conversion rate was determined through the same simulation as in Example D7.

[0263] <Comparative Example D6> Assuming a process without using a separation membrane, the membrane area per unit catalyst volume is 0 m². 2 / m 3 In addition, the conversion rate was determined through the same simulation as in Example D8.

[0264] <Comparative Example D7> Assuming a process without using a separation membrane, the membrane area per unit catalyst volume is 0 m². 2 / m 3 In addition, the conversion rate was determined through the same simulation as in Example D9.

[0265] <Comparative Example D8> Assuming a process without using a separation membrane, the membrane area per unit catalyst volume is 0 m². 2 / m 3 In addition, the conversion rate was determined through the same simulation as in Example D10.

[0266] As shown in Table D3, the results show that at any temperature, the conversion rate is higher when using a separation membrane compared to when no separation membrane is used.

[0267] [Table 7] Table D3 Example D6 250 have 82 Example D7 210 have 58 Example D8 230 have 83 Example D9 270 have 69 Example D10 290 have 52 Comparative Example D4 250 none 17 Comparative Example D5 210 none 25 Comparative Example D6 230 none 21 Comparative Example D7 270 none 11 Comparative Example D8 290 none 8

[0268] <Example D11> The film area per unit catalyst volume is 5m². 2 / m 3 In addition, the conversion rate was determined through the same simulation as in Example D6.

[0269] <Example D12> The film area per unit catalyst volume is 10m². 2 / m 3 In addition, the conversion rate was determined through the same simulation as in Example D6.

[0270] <Example D13> The film area per unit catalyst volume is 50 m². 2 / m 3 The amount of catalyst was 1000 kg. Otherwise, the conversion rate was determined by the same simulation as in Example D6.

[0271] As shown in Table D4, the results are independent of the membrane area per unit catalyst volume, and the conversion rate is higher when using a separation membrane compared to when no separation membrane is used.

[0272] [Table 8] Table D4

Claims

1. A composite material, which is formed by bonding a zeolite and an inorganic porous support composite and a dense component through an inorganic glass, said composite material being used for gas separation, wherein, The coefficient of thermal expansion of this inorganic glass is 30 × 10⁻⁶. -7 / K or higher and 90×10 -7 The temperature is below / K and the softening point is below 550℃. The inorganic glass is a lead-free inorganic glass with a lead content (PbO) of less than 10% by mass. The coefficient of thermal expansion is the average coefficient of thermal expansion measured at 30~250℃. The method for determining the softening point is as follows: the softening point is determined by a differential thermal analysis device, the sample is heated at 10℃ / min, and the second inflection point of the obtained DTA curve is taken as the softening point.

2. The bonding body according to claim 1, wherein the inorganic glass contains SnO and / or B2O3.

3. The joint according to claim 1, wherein the joint portion of the composite and the dense component is covered by a sealing membrane.

4. The bonding body according to claim 3, wherein the sealing film is a silicon dioxide film.

5. The joint according to any one of claims 1 to 4, wherein the coefficient of thermal expansion of the dense component is 30 × 10⁻⁶. -7 / K or higher and 200×10 -7 / K or below.

6. A method of using a joint, wherein the joint described in any one of claims 1 to 5 is used under high temperature conditions of 100°C to 500°C and / or high pressure conditions of 0.5 to 10 MPa.

7. A separation membrane assembly having the junction as described in any one of claims 1 to 5.

8. A reactor having the separation membrane assembly of claim 7.

9. A bonding method comprising bonding a composite of zeolite and an inorganic porous support and a dense component using inorganic glass, wherein, The composite is used for gas separation, and the coefficient of thermal expansion of the inorganic glass is 30 × 10⁻⁶. -7 / K or higher and 90×10 -7 The temperature is below / K and the softening point is below 550℃. The inorganic glass is a lead-free inorganic glass with a lead content (PbO) of less than 10% by mass. The coefficient of thermal expansion is the average coefficient of thermal expansion measured at 30~250℃. The method for determining the softening point is as follows: the softening point is determined by a differential thermal analysis device, the sample is heated at 10℃ / min, and the second inflection point of the obtained DTA curve is taken as the softening point.

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