Gas separation membrane module inspection device and inspection method

Abstract

Provided is an inspection device and an inspection method for a gas separation membrane module, which can inspect the gas separation membrane module for abnormalities such as deterioration, damage, and leaks using a small amount of gas. [Solution] The gas supplied to the gas separation membrane module is composed of one or more types of gas, After sealing either the non-permeate outlet or the permeate outlet, while continuously supplying gas to the gas separation membrane module, the non-permeate gas or the permeate gas is continuously discharged from the gas separation membrane module by at least one of pressurizing the supply side and depressurizing the permeate side, and the properties of at least one of the non-permeate gas and the permeate gas of the gas separation membrane module are measured. A method for inspecting a gas separation membrane module.

Description

[Technical Field]

[0001] The present invention relates to an inspection device and an inspection method for measuring the properties of at least one of a non-permeating gas and a permeating gas at a site of a gas separation membrane module. [Background technology]

[0002] In recent years, there has been a demand for the development of technology that can efficiently separate specific gases from a gas mixture. As a method for efficiently separating specific gases from a gas mixture, membrane separation, which utilizes differences in the gas permeability of materials to selectively allow the target component to pass through, has attracted attention. Separation membranes have been developed for a variety of gases, including helium, hydrogen, carbon dioxide, nitrogen, sulfur hexafluoride, water vapor, and rare gases. Gas separation using separation membranes is expected to be a technology that can achieve energy and space savings.

[0003] When separation membranes are used in actual separation processes, for example, flat membranes are used as spiral modules. If there are defects in the adhesive joints during module fabrication or if the separation membrane is damaged, or if the separation membrane deteriorates due to acidic gases or other factors during use, there is a risk that gas from the non-permeating side may leak into the permeating side or that separation performance may decrease. In some cases, chemical cleaning may be performed in addition to normal operation. This raises concerns that abnormalities such as damage, rupture, or deterioration of the separation membrane elements may occur, making it important to quickly detect abnormalities in the separation membrane module, identify the location of the abnormality as quickly as possible, and take early action.

[0004] Patent Document 1 discloses a method and device for evaluating the quality of a separation membrane, which measures the actual separation coefficient of a mixed gas.

[0005] Patent Document 2 discloses a method for measuring the flow rate and water quality of multiple permeates from multiple separation membrane modules arranged in series, in order to address concerns about breakage or deterioration when cleaning the separation membranes of separation membrane modules used in water treatment processes with chemicals. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 6643223 [Patent Document 2] International Publication No. 2020 / 071507 Summary of the Invention [Problem to be solved by the invention]

[0007] It is important to check for abnormalities in separation membrane modules used in actual separation processes, i.e., to inspect separation membrane modules. However, conventional methods for inspecting separation membrane modules require supplying large amounts of gas to the module for inspection. Some gases are expensive and rare, posing challenges in terms of cost and other factors.

[0008] The present invention overcomes this problem and provides an inspection device and method for a gas separation membrane module that can inspect the gas separation membrane module for abnormalities such as deterioration, damage, and leaks using a small amount of gas. [Means for solving the problem]

[0009] In order to achieve the above object, the present invention has the following configuration. (1) The gas supplied to the gas separation membrane module is composed of one or more types of gases, After sealing either the non-permeate outlet or the permeate outlet, while continuously supplying gas to the gas separation membrane module, the non-permeate gas or the permeate gas is continuously discharged from the gas separation membrane module by at least one of pressurizing the supply side and depressurizing the permeate side, and the properties of at least one of the non-permeate gas and the permeate gas of the gas separation membrane module are measured. A method for inspecting a gas separation membrane module. (2) The gas supplied to the gas separation membrane module is composed of one or more types of gases, After sealing one of the non-permeate outlet and the permeate outlet, while continuously supplying gas to the gas separation membrane module, the non-permeate gas or the permeate gas is continuously discharged from the gas separation membrane module by at least one of pressurizing the supply side and depressurizing the permeate side, and the properties of at least one of the non-permeate gas and the permeate gas of the gas separation membrane module are measured at a location within the gas separation membrane module. A method for inspecting a gas separation membrane module. (3) The method for inspecting a gas separation membrane module according to (2), wherein the characteristics of at least one of the non-permeating gas and the permeating gas are measured at two or more locations in the gas separation membrane module. (4) The method for inspecting a gas separation membrane module according to (1) or (2), wherein the gas separation membrane is a flat membrane. (5) A method for inspecting a gas separation membrane module according to (1) or (2), in which the gas separation membrane, the non-permeation side flow path material, and the permeation side flow path material are wound around a central tube that collects the permeated gas of the gas separation membrane. (6) The method for inspecting a gas separation membrane module according to (1) or (2), wherein the supply gas is composed of one type of gas. (7) A method for inspecting a gas separation membrane module according to (1) or (2), which measures one or more characteristics of the volumetric flow rate, mass flow rate, composition, temperature, pressure, and thermal conductivity of at least one of the non-permeating gas and the permeating gas. (8) An inspection device for a gas separation membrane module, comprising: a means for supplying a gas composed of one or more types of gas to the gas separation membrane module; a gas separation membrane module for separating the supplied gas into a non-permeate gas and a permeate gas; at least one of a means for pressurizing the supply side and a means for depressurizing the permeate side; a means for discharging the non-permeate gas or the permeate gas from the gas separation membrane module; and a means for measuring the characteristics of at least one of the non-permeate gas and the permeate gas from the gas separation membrane module. (9) A method for inspecting a gas separation membrane module according to (1), characterized in that it is used in at least one process selected from the following: separation of gases in the manufacturing processes of optical fibers, semiconductors, and electrical appliances; separation of gases produced by reactions of natural gas, city gas, biogas, and methanation, separation of gases containing unreacted raw materials and by-products; separation of gases produced from water electrolysis equipment; and separation of gases for concentrating a target gas from a mixed gas. (10) A method for manufacturing an optical fiber, characterized by using the gas separation membrane module inspection method of (1). (11) A method for manufacturing a semiconductor, characterized by using the gas separation membrane module inspection method according to (1). (12) A method for manufacturing an electrical product, characterized by using the gas separation membrane module inspection method of (1). (13) A gas production method characterized by using the inspection method for a gas separation membrane module of (1), which separates at least one gas selected from natural gas, city gas, biogas, gases produced by methanation reactions, gases containing unreacted raw materials or by-products, gases from fermentation or enzyme reaction processes, and gases generated from water electrolysis devices. (14) An optical fiber, characterized by being manufactured using a gas separation membrane module whose performance has been tested by the method of (1). (15) A semiconductor manufactured using a gas separation membrane module whose performance has been tested by the method of (1). (16) An electrical product characterized by being manufactured using a gas separation membrane module whose performance has been tested by the method of (1). (17) A gas separation device characterized by using a gas separation membrane module whose performance has been tested by the method of (1), which separates at least one gas selected from natural gas, city gas, biogas, gases produced by methanation reactions, gases containing unreacted raw materials and by-products, gases produced in fermentation or enzyme reaction processes, and gases produced from water electrolysis devices. [Effects of the Invention]

[0010] The present invention provides an inspection device and an inspection method for a gas separation membrane module that can inspect a gas separation membrane module for abnormalities such as deterioration, damage, and leaks using a small amount of gas. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is a schematic diagram showing an example of an inspection device for a gas separation membrane module according to the present invention. [Figure 2] FIG. 2 is a schematic diagram showing another example of an inspection device for a gas separation membrane module according to the present invention. [Figure 3] FIG. 2 is a schematic diagram showing another example of an inspection device for a gas separation membrane module according to the present invention. [Figure 4] 1 is a schematic diagram showing an example of a gas separation membrane module of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention provides a method and apparatus for inspecting a gas separation membrane module (hereinafter simply referred to as a "separation membrane module") in which the supply gas to the gas separation membrane module is composed of one or more types of gas, and after sealing either the non-permeate outlet or the permeate outlet, the gas is continuously supplied to the gas separation membrane module while continuously discharging the non-permeate gas or the permeate gas from the gas separation membrane module by at least one of pressurizing the supply side and depressurizing the permeate side, and the characteristics of at least one of the non-permeate gas and the permeate gas of the gas separation membrane module are measured.

[0013] Hereinafter, embodiments of the present invention will be described in detail.

[0014] The gas separation membrane module inspection device of the present invention comprises: (1) A means for sealing either the non-permeate outlet or the permeate outlet of a gas separation membrane module after supplying a feed gas consisting of one or more gases to the gas separation membrane module. (2) A gas separation membrane module that separates a feed gas consisting of one or more gases into a non-permeate gas and a permeate gas. (3) At least one of pressurizing the supply side and depressurizing the permeation side while continuously supplying gas to the gas separation membrane module. (4) A gas discharge means for continuously discharging non-permeated gas or permeated gas from the gas separation membrane module. (5) A means for measuring the characteristics of non-permeable or permeable gases through gas separation membranes. It has.

[0015] <Means for supplying gas to separation membrane module> The present invention has a means for supplying a feed gas composed of one or more gases to a separation membrane module, in which a pipe or the like is connected to a flow path on the feed gas side of the separation membrane module, and the feed gas is passed through the pipe or the like.

[0016] In conventional inspection methods, in which gas is continuously supplied and vented to a separation membrane module without sealing either the non-permeate or permeate outlet, the amount of gas used increases in proportion to the inspection time, and costs also increase, especially when expensive gases are used. For example, the performance of a separation membrane can be determined by observing its air separation characteristics. However, in the case of a separation membrane used to separate expensive gases such as helium, which have smaller kinetic molecular diameters than nitrogen and oxygen, rather than nitrogen and oxygen, which are the main components of air, it is preferable to reduce the amount of gas used for inspection. The same is true for separation membranes used to separate expensive gases such as sulfur hexafluoride, which have larger kinetic molecular diameters than nitrogen and oxygen.

[0017] Furthermore, when using a sealed gas, for example, if the gas is supplied into the separation membrane module and then the non-permeation side and the supply side are sealed, and testing is performed using the gas sealed in the separation membrane module without continuously supplying gas, the amount of gas used can be reduced because the gas supply is stopped during testing.However, when the sealed gas is discharged and the pressure difference that acts as the driving force for permeation becomes small, measurement becomes difficult, and therefore, it may be necessary to perform the test before the permeation flow rate stabilizes, or the test may have to be repeated without identifying the location of the leak.

[0018] Therefore, in the present invention, by sealing either the non-permeate outlet or the permeate outlet and continuously supplying gas while performing the inspection, it is possible to reduce the amount of gas used during the inspection while ensuring sufficient inspection time to identify the leak location. When the non-permeate outlet is sealed, the supplied gas is converted into permeate gas by the separation membrane and discharged, eliminating gas that is wasted from the non-permeate side, making it possible to perform the inspection with the minimum necessary supply flow rate. Similarly, when the permeate outlet is sealed, only non-permeate gas is discharged by the separation membrane, making it possible to perform the inspection with the minimum necessary supply flow rate.

[0019] The material of the piping and the like can be determined depending on the properties of the gas to be supplied, and for example, metals such as stainless steel and copper, and organic materials such as polypropylene, polyethylene, and fluororesin can be used.

[0020] In addition, instruments such as a flow meter, a pressure meter, a thermometer, and a hygrometer may be provided to monitor the ventilation state of the supply gas.

[0021] Furthermore, a device such as a valve for controlling the flow rate of the supply gas may be provided, and a pressure control device such as a compressor for controlling the pressure of the supply gas may be provided.

[0022] Storage means such as tanks or cylinders may also be provided for storing the supply gas, and these storage means may be temperature and pressure controlled.

[0023] By increasing the pressure in the storage means, at least a part of the supply gas can be stored as a liquid. In this case, a mechanism can be provided to reduce the pressure and convert the liquid into a gas when supplying the gas to the separation membrane module.

[0024] When the pressure is increased in the storage means to liquefy only the water vapor, the liquefied water can be separated and removed.

[0025] Furthermore, particularly when circulating at least some or all of the non-permeating gas and / or permeating gas of the separation membrane module in a storage means such as a tank, agitating blades or the like for mixing the gases can be provided in the storage means such as a tank in order to mix the gases as uniformly as possible with the gas stored in the tank and supply the gas to the separation membrane module.

[0026] The type of gas to be supplied is not particularly limited, and examples thereof include gases such as helium, hydrogen, ammonia, nitrogen, oxygen, argon, methane, carbon dioxide, and water vapor.

[0027] The supply gas may be a mixture of two or more types, or may be a single type. However, since the composition of the gas in each part of the module is uniquely determined, it is preferable to use a single type of supply gas. In this specification, "the supply gas is composed of one type of gas" means that when multiple tests are performed using a mass spectrometer or the like, the second component or components of the supply gas supplied in each test are less than 0.001 mol%, and the type of supply gas may be changed for each test throughout the entire test. Furthermore, "a supply gas composed of two or more types of gases" means that the supply gas contains 0.001 mol% or more of each gas as determined by analysis using a mass spectrometer or the like. When selecting the type of gas, the dynamic molecular diameter may be used as an indicator in the case of gas separation using a molecular sieve, except for separation membranes where dissolution and diffusion must be taken into consideration.

[0028] Gases with smaller kinetic molecular diameters are more likely to permeate separation membranes, while gases with larger kinetic molecular diameters are less likely to permeate separation membranes. The gas used for testing can be selected according to the separation characteristics of the target separation membrane.

[0029] For example, when gases with different kinetic molecular diameters are supplied, if there are areas where gases with smaller kinetic molecular diameters are more permeable, while gases with larger kinetic molecular diameters have no change in permeability, the degree of abnormality can be grasped.

[0030] When using gases with different kinetic molecular diameters, it is preferable that the ratio of the kinetic molecular diameters of the larger gas and the smaller gas be within a certain range, as this makes it easier to grasp the degree of abnormality. Specifically, it is preferable that the ratio be 1.05 or more and 2.60 or less. More preferably, it is 1.10 or more and 2.55 or less, and even more preferably, it is 1.20 or more and 2.50 or less.

[0031] When selecting the type of gas, permeability may be used as an index.

[0032] In measuring the permeability, the permeability may vary depending on the location of the separation membrane module and due to issues with the accuracy of the measurement method.

[0033] Therefore, from the viewpoint of grasping the degree of abnormality, when gases with different permeabilities are supplied, the ratio of the permeabilities of the gas with the higher permeability and the gas with the lower permeability can be calculated by Equation 1, and is preferably 1.1 or more and 2000 or less, more preferably 3 or more and 1500, and even more preferably 10 or more and 1000 or less. Formula 1: Permeability ratio = (permeability of gas with high permeability) ÷ (permeability of gas with low permeability) In the case of a gas that is easily condensed, the substance may be kept at a constant temperature, or the degree of vacuum may be adjusted to allow the substance to exist as a gas.

[0034] There are no particular limitations on the temperature, pressure, flow rate, etc. of the gas supplied in the supply step, and any conditions that are compatible with the specifications of the supply step and the separation membrane module in the next step can be applied.

[0035] Before the gas is supplied to the next separation membrane module, it may be subjected to pretreatment such as filtering, moisture absorption, or humidification.

[0036] <Gas separation membrane module> In the present invention, at least one gas permeates the separation membrane in the separation membrane module.

[0037] (Partial pressure difference) In a membrane separation mechanism, the driving force for separation when a gas permeates through a gas separation membrane is mainly the partial pressure difference between the non-permeation side and the permeation side of the gas separation membrane.

[0038] In the present invention, this partial pressure difference can be generated by reducing the pressure on the permeate side of the separation membrane. The degree of reduction in pressure can be set according to the specifications of the separation membrane, etc., in order to obtain the desired separation efficiency.

[0039] Generally, the greater the degree of vacuum, the greater the partial pressure difference between the non-permeate side and the permeate side, improving separation efficiency. When using a vacuum pump, a degree of vacuum close to vacuum can be achieved, but there are issues such as increased pump load and energy consumption, and high equipment and electricity costs. To reduce the load and energy consumption of the vacuum pump, it is sometimes possible to operate it at around 20 to 50 kPa.

[0040] In the case of reduced pressure, it is not possible to obtain a partial pressure difference equal to or greater than an absolute vacuum, but the non-permeation side can be pressurized to obtain the desired partial pressure difference. The non-permeation side is pressurized by pressurizing the feed gas and supplying it to the separation membrane module.

[0041] In the present invention, the supply gas may contain water vapor, but the partial pressure difference is limited by the vapor pressure of water at the operating temperature.

[0042] For example, a water vapor pressure of approximately 3 kPa occurs at a water temperature of 25°C, and approximately 2 kPa occurs at a water temperature of 20°C. However, if the pressure is reduced to about 90 kPa, a partial pressure difference almost equal to that of an absolute vacuum can be obtained.

[0043] Alternatively, both the pressure on the permeation side of the separation membrane and the pressure on the feed gas may be applied. The degree of pressure application can be set according to the specifications of the separation membrane in order to obtain the permeability of the feed gas composed of one or more gases through the separation membrane, and either method can be applied.

[0044] As a method for pressurization, any commonly used method such as a compressor can be applied.

[0045] Any of the above means can create the necessary partial pressure difference.

[0046] (separation membrane) In the present invention, various separation membranes can be used.

[0047] The separation membrane can be appropriately selected depending on the type of gas and the conditions of use. Separation membranes similar to those commonly used in the relevant technical field can be used without particular limitation. Examples include polymer membranes made of rubber-like polymer materials such as silicone resin and polybutadiene resin, cellulose acetate, polysulfone, aromatic polyamide, polyethersulfone, polyacrylonitrile, polyphenylene sulfide, polyetheretherketone, polytetrafluoroethylene, and polyvinylidene fluoride, as well as inorganic membranes containing metals such as zeolite, silica, and palladium.

[0048] The separation membrane may be any of a homogeneous membrane, an asymmetric membrane consisting of a homogeneous layer and a porous layer, a microporous membrane, and the like.

[0049] When relatively small gases such as hydrogen and helium are to be permeated, polyamide membranes, silica membranes, carbon membranes, zeolite membranes, graphene membranes, polyimide resins, fluorine-based ion exchange membranes, polyetherimide resins, polysulfone-based resins, etc. can be used.

[0050] The separation membrane may also have a coating layer. Separation membranes have a small number of regions with significantly high gas permeability, such as coarse pores and defects. In these regions, the contribution of molecular sieving to separation is small, and the selective separation ability for gases with small molecular diameters, such as hydrogen, helium, water vapor, and ammonia, is low. Reducing the contribution of regions with low selective separation ability, such as coarse pores and defects, is preferable for improving the selective separation ability of the entire membrane, and forming a coating layer on the separation membrane can suppress gas permeation through coarse pores and defects. While the permeation of oxygen, nitrogen, methane, etc. is significantly suppressed, the effect on the permeation of light gases such as hydrogen and helium is small, thereby significantly improving the selective separation ability.

[0051] The coating layer does not necessarily need to cover the entire surface of the separation membrane; there may be cases where the coating layer is partially missing due to unevenness in the coating when the coating layer is formed, or where the coating layer is formed only on surfaces with particularly many coarse pores or defects.

[0052] The coating layer can be made of any material commonly used in the art, without any particular limitations, including organic materials such as silicone resin, polyolefin resin, polyvinyl alcohol, and polyurethane, as well as metal-organic frameworks (MOFs), and metal-based materials using palladium or palladium alloys as hydrogen-permeable materials.

[0053] (Separation membrane module) In the separation membrane module, the feed gas is passed through the inlet of the separation membrane module and continuously passed toward the outlet of the separation membrane module, where it is filtered by the separation membrane.

[0054] In this case, if two or more types of gas are supplied, some components will permeate the permeation side of the separation membrane, and the components that do not or have difficulty permeating the separation membrane will be concentrated on the non-permeation side of the separation membrane module. As a result, the partial pressure of the components that permeate the separation membrane will decrease, making it difficult for the gas to permeate.

[0055] Even when the feed gas is one type of gas, a portion of it will permeate the separation membrane and become a permeated gas, while the remainder will become a non-permeated gas.

[0056] Here, the concentration polarization on the membrane surface, which becomes the permeation resistance, is preferably eliminated by increasing the flow rate of the supply gas while taking into consideration the diffusion of the supply gas. Methods for this include thinning the non-permeation side flow path material or, in the case of flat membranes, feeding the supply gas from the end face of the separation membrane module and discharging it from the outer periphery.

[0057] When gas is passed through a separation membrane module, the module may have a structure in which the permeate gas flows in a parallel or countercurrent direction to the supply gas, a cross-flow structure in which the supply gas and permeate gas flow in different directions by 90°, or a structure in which the supply gas and permeate gas flow in the same direction. Furthermore, a combination of these structures is also possible, and any of these flow path structures can be applied.

[0058] The separation membrane may be modularized and housed in a container for use. The separation membrane module may be of any type, such as a flat membrane type, a plate and frame type, a spiral type, a hollow fiber membrane type, a tubular type, or a pipe type.

[0059] (Spiral-wound gas separation membrane module) As shown in Figures 1, 2, 3, and 4, a spiral-wound gas separation membrane module 100 according to one embodiment of the present invention comprises a central tube 6, separation membrane leaves wound around the central tube 6, a non-permeate side channel material 2, and a permeate side channel material 3. This separation membrane module 100 is loaded into a pressure vessel 7 for use. The x-axis direction in Figure 4 is the longitudinal direction of the central tube 6. The y-axis direction is perpendicular to the longitudinal direction of the central tube 6.

[0060] The central tube 6 is a hollow (cylindrical) member that is open at least at the downstream end so that the permeate gas described below can be discharged. When multiple gas separation membrane modules 100 are connected, a central tube 6 that is open at both ends is used. Multiple holes are provided on the side surface of the central tube 6 (the side surface of the cylindrical shape).

[0061] The separation membrane leaf has a non-permeate side surface and a permeate side surface, and comprises a plurality of separation membranes 1 arranged with their non-permeate side surfaces facing each other and their permeate sides facing each other, and a non-permeate side flow path material 2 arranged between the non-permeate side surfaces of the separation membranes 1. Note that, for example, one membrane is folded with its permeate side or non-permeate side surface facing inward and wrapped around a central tube 6. This also includes the case where a plurality of membranes are each folded with their permeate side or non-permeate side surface facing inward and wrapped around a central tube 6.

[0062] Furthermore, a permeate-side channel material 3 is disposed between the permeate-side surfaces of the separation membranes 1 and is wrapped around a central tube 6 together with the separation membrane leaves to form a gas separation membrane module 100 .

[0063] A supply gas 201 is supplied from one end face of the gas separation membrane module 100. The supply gas 201 is separated while moving within the gas separation membrane module 100 along the longitudinal direction of the central tube 6, and permeated gas 202 that has permeated the separation membrane passes through the interior of the central tube 6 from holes in the side of the central tube 6 and is discharged from its end. The unfiltered supply gas is discharged from the other end face of the gas separation membrane module 100 as non-permeated gas 203.

[0064] The gas separation membrane module of the present invention includes a non-permeate-side channel material and a permeate-side channel material. Examples of such channel materials include nets and nonwoven fabrics, as well as knitted fabrics such as tricot, woven fabrics such as plain weave mesh, and porous sheets with protrusions, such as textured sheets. The protrusions that function as channel materials may be fixed to the non-permeate-side or permeate-side surface of the separation membrane.

[0065] The non-permeate side channel material and the permeate side channel material may be the same or different in material, shape, and average pore size.

[0066] As a material for molding or forming the non-permeate side flow path material and the permeate side flow path material, a thermoplastic resin is preferred from the viewpoint of moldability, and from the viewpoint of suppressing damage to the separation membrane, polyester, nylon, polyphenylene sulfide, polyethylene, polypropylene, polysulfone, polyethersulfone, polylactic acid, ABS (acrylonitrile-butadiene-styrene) resin, or UV-curable resin is more preferred.

[0067] The ends of the separation membrane sandwiching the non-permeation side flow path material are appropriately sealed together. Examples of the "sealing" method include adhesion using an adhesive or hot melt, fusion using heat or a laser, or sandwiching a rubber sheet, but simple sealing by adhesion is preferred.

[0068] There are no particular limitations on the shape of the central tube 6, but as mentioned above, a cylindrical shape can be used, and the outer periphery has one or more holes through which gas can pass. Alternatively, a partition wall may be provided inside the central tube 6, so that gas sealed at one end cannot move to the other end, but must pass through the holes provided on the outer periphery.

[0069] (Arrangement of separation membrane modules) A single separation membrane module may be used, or multiple modules may be used. When multiple separation membrane modules are used for each, the separation membrane modules may be arranged in parallel or series, or may be arranged in a tree configuration in which the number of separation membrane modules in the second non-permeate stage is reduced from the number of separation membrane modules in the first non-permeate stage. Furthermore, these separation membrane modules may be provided with a circulation flow in which at least one of the non-permeate gas or permeate gas from some or all of the separation membrane modules is combined with the supply gas to the separation membrane module or the supply gas to the separation membrane module in the preceding stage.

[0070] (Pressure of gas supplied to separation membrane module) In the present invention, the supply gas to the separation membrane module may be pressurized. By pressurizing the supply gas and supplying it to the separation membrane module, the non-permeation side is pressurized. This generates a pressure difference between the permeation side and the non-permeation side, providing a driving force for permeation through the separation membrane.

[0071] The gas to be supplied may be pressurized using a device such as a compressor, or the gas may be supplied from a high-pressure container such as a cylinder.

[0072] (Depressurization on the permeation side of the separation membrane module) In the present invention, the permeate side of the separation membrane module may be depressurized. A vacuum pump may be used for depressurization. Alternatively, an aspirator or ejector may be used. However, it is necessary to consider the possibility that the gas permeating through the separation membrane may come into contact with the driving fluid of the aspirator or ejector, resulting in mixing or dissolution.

[0073] The vacuum pump, aspirator, and ejector may be the same as those commonly used in the art without any particular limitations.

[0074] The vacuum pump may be of any type, such as a diaphragm type or an oil type.

[0075] Aspirators and ejectors are known to be made of metal or resin. The material can be selected based on the durability and temperature of the gas used. When the driving fluid of an aspirator or ejector is a liquid, various liquids such as water, an aqueous solution of dissolved salts, silicone, or a mixture of these can be used. When the driving fluid of an aspirator or ejector is a gas, various gases or a mixture of these can be used.

[0076] The degree of pressure reduction is preferably set within a range in which most of the gas on the permeation side does not condense. A large degree of pressure reduction is also preferable because it increases the driving force for separation when the gas permeates through the gas separation membrane. The degree of pressure reduction may be adjusted, including the possibility of pressurizing the supply gas.

[0077] (Sealing the outlet of the separation membrane module) The outlets on the non-permeate side and permeate side of the separation membrane module may be sealed with valves, three-way valves, closing plates, check valves, etc. Valves may be provided in the line for supplying a predetermined gas, the line for discharging the non-permeate gas, and the line for discharging the permeate gas. In consideration of gas leakage, it is more preferable to provide multiple valves.

[0078] In the present invention, either the non-permeation side or permeation side outlet of the separation membrane module is sealed, and at least one of pressurization of the supply side and depressurization of the permeation side is carried out while continuously supplying gas. For example, it is possible to reduce the pressure on the permeate side of the separation membrane module, supply gas, and then seal both the non-permeate and permeate outlets to measure the pressure change on the permeate side and perform an inspection based on the trend. However, this raises concerns that the measurement time may become too short, making stable inspection difficult.

[0079] The non-permeate side of the separation membrane module is sealed by supplying a predetermined supply gas to the separation membrane module using gas supply means 101 and then closing valve 12C. The permeate side of the separation membrane module is sealed by supplying a predetermined supply gas to the separation membrane module using gas supply means 101 and then closing valve 12B.

[0080] If another gas is present in the separation membrane module, a specified gas is supplied to the separation membrane module to replace the gas before sealing. During replacement, valves 12A, 12B, and 12C are opened to supply the specified supply gas to the separation membrane module. At this time, it is necessary to replace the volume of the separation membrane module and the volume of the container in which the separation membrane module is installed with the specified supply gas, so it is preferable to supply a larger amount of supply gas.

[0081] For example, when supply gas is passed through a pressure vessel loaded with a separation membrane module, if a perfectly mixed flow is assumed, a gas volume several times larger than the volume of the non-permeated side is supplied. If a push flow is assumed, a gas volume of at least one time is supplied. These values ​​can be determined taking into consideration the structure of the separation membrane module and the vessel in which the separation membrane module is loaded.

[0082] When replacing the air with the predetermined gas, the separation membrane module may be depressurized once, and other gases may be discharged from the separation membrane module or the container in which the separation membrane module is mounted, before supplying the predetermined gas. In this method, the predetermined gas is supplied in the absence of almost any other gases, and therefore the required amount of the predetermined gas can be reduced.

[0083] Here, the replacement with a specified gas does not have to be strictly 100% replacement. For example, if there is air in a separation membrane module and it is replaced with helium, strictly 100% replacement is preferable, but even if there is a few ppm of air in the separation membrane module, it is acceptable as long as it does not significantly affect the measurement after sealing. For example, even if 0.01% air remains in the separation membrane module, the effect on the measurement after sealing is 0.01%, and a difference of a few percent in the measurement results between a normal separation membrane module and a defective separation membrane module is acceptable for inspection.

[0084] After the replacement of the gas inside the module is completed, the valve 12C is closed if the non-permeation side is to be sealed, and the valve 12B is closed if the permeation side is to be sealed.

[0085] Whether to seal the non-permeation side or the permeation side can be appropriately selected depending on the properties of the feed gas, etc. Either side may be sealed.

[0086] (Pressure and depressurization of separation membrane module) In the present invention, a gas is supplied to the separation membrane module, and the outlet on the non-permeation side or the permeation side is sealed, and then at least one of pressurization on the supply side and depressurization on the permeation side is carried out.

[0087] If the separation membrane has a defect, the amount of permeation through the membrane will be higher than that of a normal separation membrane. Also, if there is a defect in a part of the separation membrane module, such as the adhesive joint, gas will leak from that part, causing more gas to move to the permeation side and increasing the flow rate.

[0088] As described above, a large amount of gas moves from the non-permeate side to the permeate side at the defective site. For example, if the permeate side is sealed, the extent of the defect can be detected by comparing the flow rate inside the module or at the outlet on the non-permeate side with that of a normal module. If the non-permeate side is sealed, the extent of the defect can be detected by comparing the permeate flow rate inside the module on the permeate side or at the outlet with that of a normal module.

[0089] Furthermore, when pressurization is performed with at least the permeation side outlet sealed, the movement of gas from the non-permeation side to the permeation side in a defective separation membrane module is greater than in a normal separation membrane module, so by comparing the permeation side pressure after a certain period of time, it is possible to distinguish between a normal separation membrane module and a defective separation membrane module.

[0090] In the present invention, when at least one of pressurization and decompression of the separation membrane module is performed, the pressure that serves as the driving force for the separation membrane can be set taking into consideration the permeability of a predetermined gas, the characteristics of the separation membrane, etc., and either pressurization only, decompression only, or both pressurization and decompression can be selected.

[0091] In the present invention, when depressurizing the separation membrane module, the non-permeation side is sealed, valve 12A is opened to continuously supply gas while valve 12B is opened, and the permeation side of the separation membrane module is depressurized with a vacuum pump, whereby membrane separation is performed using the pressure as a driving force.

[0092] In the present invention, when pressurizing a separation membrane module and sealing the non-permeate side, first, gas is supplied to the separation membrane module as described above, and the non-permeate side is sealed by closing valve 12C. Next, pressure can be applied by supplying the same gas as that supplied to the module while keeping valve 12A open. The degree of pressure application can be adjusted by adjusting the supply flow rate and the opening of valve 12B.

[0093] In the present invention, when pressurizing a separation membrane module and sealing the permeate side, first, gas is supplied to the separation membrane module as described above, and the permeate side is sealed by closing valve 12B. Next, valve 12A is left open, and the same gas as that supplied to the module is supplied to pressurize the module. The degree of pressurization can be adjusted by the supply flow rate and the opening of valve 12C.

[0094] <Non-permeate gas discharge means and permeate gas discharge means> The present invention may have non-permeate gas and permeate gas discharge means 102 for discharging the non-permeate gas and permeate gas, respectively, from the gas separation membrane module. In this non-permeate gas and permeate gas discharge means 102, piping or the like is connected to a flow path on the non-permeate gas discharge side and a flow path on the permeate gas discharge side of the separation membrane module, and all or a portion of at least one of the non-permeate gas or the permeate gas is vented to a means for measuring the properties of at least one of the non-permeate gas or the permeate gas.

[0095] The material of the piping and the like can be determined depending on the properties of the gas to be supplied, and for example, metals such as stainless steel and copper, and organic materials such as polypropylene, polyethylene, and fluororesin can be used.

[0096] In addition, instruments such as a flow meter, a pressure meter, a thermometer, and a hygrometer may be provided to monitor the ventilation state of at least one of the non-permeating gas and the permeating gas.

[0097] Furthermore, a device such as a valve for controlling the flow rate of at least one of the non-permeate gas and the permeate gas may be provided, and a pressure control device such as a compressor for controlling the pressure of at least one of the non-permeate gas and the permeate gas may be provided.

[0098] Storage means such as a tank or cylinder may be provided for storing at least one of the non-permeating gas and the permeating gas, and these storage means may be capable of controlling the temperature and pressure.

[0099] By increasing the pressure in the storage means, at least a portion of the non-permeating gas or at least one of the permeating gas can be stored as a liquid. In this case, a mechanism can be provided to reduce the pressure and convert the liquid into a gas when the non-permeating gas or at least one of the permeating gas is supplied to a means for measuring the properties of the non-permeating gas or at least one of the permeating gas.

[0100] When the pressure is increased in the storage means to liquefy only the water vapor, the liquefied water can be separated and removed.

[0101] Furthermore, particularly when circulating some or all of the non-permeate gas and / or permeate gas of the separation membrane module in a storage means such as a tank, a stirring blade or the like for mixing the gases can be provided in the storage means such as a tank so that the gases can be mixed as uniformly as possible with the gases stored in the tank and supplied to a means for measuring the properties of at least one of the non-permeate gas or the permeate gas.

[0102] There are no particular limitations on the temperature, pressure, flow rate, etc., at the time of discharging at least one of the non-permeating gas and the permeating gas, and any conditions that meet the specifications of the means for measuring the properties of at least one of the non-permeating gas and the permeating gas can be applied.

[0103] Furthermore, the gas may be subjected to pretreatment such as filtering, moisture absorption, or humidification before being supplied to a means for measuring the properties of the non-permeating gas or permeating gas.

[0104] <Means for measuring the properties of non-permeable or permeable gases> The present invention has means 103 for measuring the characteristics of at least one of the non-permeating gas and the permeating gas of the gas separation membrane at the site of the gas separation membrane module.

[0105] (Properties of at least one of non-permeable gas and permeable gas) In the present invention, the separation membrane module is diagnosed by measuring at least one of the properties of the non-permeating gas or the permeating gas. Examples of at least one of the properties of the non-permeating gas or the permeating gas include volumetric flow rate, mass flow rate, temperature, pressure, composition, thermal conductivity, odor, weight, specific gravity, specific heat, color, liquefaction temperature, liquefaction pressure, radiation, diffusion coefficient, solubility in water and water containing solutes, pH at dissolution, solubility in organic solvents, etc., heat of combustion, calorific value, recovery rate of a specific gas, and pressure on the permeating gas side. The module has a means for measuring at least one of these properties.

[0106] These properties can be temporarily changed by varying one or more of the following: volumetric flow rate, mass flow rate, temperature, pressure, composition, thermal conductivity, odor, weight, specific gravity, specific heat, color, liquefaction temperature, liquefaction pressure, radiation, diffusion coefficient, solubility in water and water containing solute, pH and electrical conductivity at dissolution, solubility in organic solvents, heat of combustion, calorific value, recovery rate of specific gas, and pressure on the permeate gas side. For example, a step response may be used to change the properties and measure the response.

[0107] The water containing the solute may be a salt such as sodium chloride, magnesium sulfate, or ammonium chloride, an ionic liquid, or an organic substance such as glucose, or may be a mixture with an organic solvent such as ethanol, hexane, carbon tetrachloride, benzene, or acetone.

[0108] Considering the necessary equipment, cost, ease of measurement, quantitativeness, etc., one or more of the following characteristics are preferred: volumetric flow rate, mass flow rate, composition, temperature, pressure, and thermal conductivity.

[0109] For example, in a defective separation membrane module, the permeate volumetric flow rate is higher than normal at the defective site. Therefore, by measuring the permeate volumetric flow rate at the outlet of the separation membrane module after a predetermined time when sealing the non-permeate side, or the non-permeate sediment flow rate at the outlet of the separation membrane module after a predetermined time when sealing the permeate side, and comparing these values ​​with those of a normal separation membrane module, the presence or absence of a defect can be determined. Furthermore, by measuring the permeate volumetric flow rate at each site within the separation membrane module and comparing the normal and defective separation membrane modules, the presence or absence of a defect can be inferred. Furthermore, when two or more types of gas are used, the presence or absence of a defect can be determined by measuring the permeate gas composition at the outlet of the separation membrane module and comparing it with that of a normal separation membrane module. Furthermore, by measuring the composition at each site within the separation membrane module and comparing the composition of a normal separation membrane module with that of a defective separation membrane module, the presence or absence of a defect can be inferred. Furthermore, when pressurizing with either the non-permeate or permeate outlet sealed, the movement of gas from the non-permeate side to the permeate side in a defective separation membrane module is greater than in a normal separation membrane module. Therefore, by comparing the permeate side pressure after a certain time, normal and defective separation membrane modules can be distinguished.

[0110] (measurement means) In the present invention, the volumetric flow rate, mass flow rate, temperature, pressure, composition, thermal conductivity, odor, weight, specific gravity, specific heat, color, liquefaction temperature, liquefaction pressure, radiation, diffusion coefficient, solubility in water and water containing solute, pH at dissolution, solubility in organic solvents, etc., heat of combustion, calorific value, recovery rate of specific gas, and pressure on the permeating gas side can be measured by commonly known methods and are not limited to any particular technique.

[0111] In the case of producing a separation membrane module, taking into consideration the necessary equipment, cost, ease of measurement, quantitativeness, etc., one or more of the following characteristics are preferred: volumetric flow rate, mass flow rate, composition, temperature, pressure, and thermal conductivity.

[0112] For volumetric flow, flow meters such as float type and soap film type can be applied. For mass flow, flow meters such as mass flow meters can be applied. For composition, gas chromatography can be applied. Gas chromatography using a thermal conductivity detector can also be applied. For temperature, both contact and non-contact types can be applied. For contact types, thermocouples, platinum resistance thermometers, thermistor thermometers, bimetal thermometers, liquid-filled thermometers, and mercury thermometers can be applied. For non-contact types, radiation temperature sensors and color temperature sensors can be applied. For pressure, diaphragm types, piezoelectric types, piezo-resistance types, pitot tube types, and manometers that detect differential pressure can be applied. Any sensor for absolute pressure, gauge pressure, or differential pressure can be applied.

[0113] The more characteristics that are measured, the better from the viewpoint of determining the presence or absence of abnormalities and their severity. On the other hand, it is preferable to select the items to be measured, since this makes the analysis complicated and it is difficult to determine the purity when only one type of gas is supplied.

[0114] Here, when measuring each characteristic, a sensor may be provided inside the separation membrane module for measurement, or a wireless tag (RFID tag), sensor, or the like may be provided. Here, the sensor may be attached to the separation membrane module at the time of manufacturing the separation membrane module, or may be attached at the time of measurement.

[0115] When the sensor is attached during the manufacture of the separation membrane module, the change in the sensor may be measured in real time, or, for example, the adsorbent may be placed inside the module and removed at intervals to measure the amount of adsorption.

[0116] The advantage is that it is easy to put on and the position of the device can be easily adjusted.

[0117] When attached during measurement, the sensor is inserted into the structure of the separation membrane module, so it is preferable that the sensor is small and has low rigidity so as not to damage the structures inside the separation membrane module, such as the separation membrane and flow path material. The sensor may be attached while visually observing the inside of the separation membrane module using a small camera commonly used in medical applications.

[0118] As is common to the following examples, a scale or marking may be attached inside the separation membrane module to enable confirmation of the sensor position. In this case, rather than attaching the scale or marking to the separation membrane itself, the scale or marking may be attached to the pressure vessel in which the separation membrane is loaded or, in the case of a spiral-type separation membrane module, inside the central pipe which is the flow path for the permeate gas. Furthermore, a scale or markings may be attached to the outside of the separation membrane module, in which case the length of the inserted wiring or the like can be checked from outside the separation membrane module, thereby enabling the position to be confirmed.

[0119] A transparent or translucent pressure vessel may be prepared to identify and mark the insertion position of the sensor.

[0120] Furthermore, since there is a space limitation inside the separation membrane module, at least one of the non-permeated gas and the permeated gas may be sampled inside the separation membrane module and discharged to the outside of the separation membrane module for measurement.

[0121] At least one of the non-permeated gas and the permeated gas is preferably collected at two or more locations in the separation membrane module.

[0122] A plurality of pipes for collecting gas may be arranged inside the separation membrane module.

[0123] Alternatively, one or a limited number of pipes or the like may be arranged within the separation membrane module, and the position within the separation membrane module may be changed to allow gas to be sampled at a plurality of locations.

[0124] The location where the permeate gas is sampled may be one location. In this case, the cause of the abnormality is assumed to some extent, and measurement is performed at that location. The presence or absence of an abnormality can be determined by comparing with a product that is not abnormal. For example, in the case of a spiral-wound separation membrane module, if a defect in the adhesive that seals the separation membrane is assumed, the adhesive can be measured.

[0125] When collecting gas, it is preferable to avoid mixing it with gas from other sites as much as possible.

[0126] For example, when sampling permeated gas in a spiral separation membrane module, the position of the gas sampling port may be changed along the length of the central tube 6, and the gas may be sampled through a gas sampling pipe. In this case, if the gas sampling port is sealed to fit the inner diameter of the central tube 6, almost all of the gas flowing into the central tube 6 can be sampled.

[0127] For sealing, commonly used sealing materials can be used, such as O-rings and packing made of silicone, butyl rubber, Teflon (registered trademark), etc. In this case, almost all of the permeable gas passing through from the upstream of the central tube 6 is sampled, but by sampling the gas from the most upstream part and checking the characteristics of that gas, any abnormal areas along the way can be identified.

[0128] Depending on the structure of the separation membrane module, it may be difficult to insert a pipe for gas sampling. In such cases, a thin silicone tube with an outer diameter of about 1 mm or a hollow fiber tube with an outer diameter of several hundred μm may be used.

[0129] In the case of such a thin tube, it may take time to collect the gas, so it may be possible to use a vacuum pump or the like to suck the gas.

[0130] Considering the gas sampling operation, the flow rate of the permeating gas is preferably at least a certain level.

[0131] By reducing the cross-sectional area of ​​the flow path of the piping through which the gas discharged from the separation membrane module passes, the flow rate of the gas can be increased and the backflow of the gas can be reduced. If the resistance to ventilation becomes large, a vacuum pump or the like may be used as an aid.

[0132] Gases generally have a larger diffusion coefficient than liquids. Therefore, it is preferable that the flow of gases, including the supply gas, non-permeating gas, and permeating gas of a separation membrane module, is dominant until the gases are discharged from the separation membrane module. It is preferable to appropriately set the flow rate, flow velocity, temperature, viscosity, and other parameters of the gases.

[0133] In particular, the flow rate and flow velocity of the gas are preferably large as long as they do not cause problems with pressure loss in the separation membrane module. Here, the flow velocity of the gas can be calculated from the flow rate of the gas and the cross-sectional area of ​​the flow path in the separation membrane module.

[0134] (Separation membrane module diagnosis) Here, the diagnosis of a separation membrane module using the testing device and method of the present invention will be described.

[0135] When diagnosing a separation membrane module using the inspection device of the present invention, if only one type of gas is supplied, the inspection is performed using a gas with a large dynamic molecular diameter or a gas with low permeability, and if there is a region where the permeability is higher than normal, that region is considered to be abnormal.

[0136] In particular, if high permeability is obtained even when a gas that is almost impermeable is supplied, it is possible that there is an abnormality such as physical damage.

[0137] Here, the detection of the above permeability may be performed by, for example, measuring whether there is a region on the permeation side where the flow rate increases, or conversely, measuring whether there is a region on the non-permeation side where the flow rate decreases. Either method that is easier to measure may be selected based on the material balance.

[0138] When testing is performed with a gas having a small kinetic molecular diameter or a gas having a high permeability, the direction of increase in permeability is similar, but the rate of change may be lower because the permeability is originally high, although this is influenced by factors such as the type of separation membrane and the separation mechanism. Therefore, it is preferable to perform testing with a gas having a large kinetic molecular diameter and then with a gas having a small kinetic molecular diameter or a gas having a high permeability. When supplying a gas composed of two or more types of gases with different kinetic molecular diameters, if there are areas where the gas with the small kinetic molecular diameter permeates more, while the permeability of the gas with the large kinetic molecular diameter remains unchanged, the degree of abnormality can be determined.

[0139] Here, if gases with similar permeability are selected as supply gases, the behavior regarding permeation will be similar, making it difficult to grasp the degree of abnormality.

[0140] In measuring the permeability, the permeability may vary depending on the location of the separation membrane module and due to issues with the accuracy of the measurement method.

[0141] Therefore, from the viewpoint of grasping the degree of abnormality, when gases with different permeabilities are supplied, it is preferable that the ratio of the permeabilities of the gas with higher permeability to the gas with lower permeability is large.

[0142] In the present invention, various separation membranes having at least a separation functional layer can be used. The separation membrane may have a coating layer. When the coating layer is used, the presence or absence of an abnormality can be more clearly determined by using gases with different separation properties for the separation functional layer and the coating layer.

[0143] The technology of the present invention can be used in at least one process selected from the following: separation of gases in the manufacturing processes of optical fibers, semiconductors, and electrical products; separation of gases produced by reactions such as natural gas, city gas, biogas, and methanation, separation of gases containing unreacted raw materials and by-products; separation of gases generated from water electrolysis equipment, and separation of gases to concentrate a target gas from a mixed gas.

[0144] The technique of the present invention may be used to inspect a separation membrane module used in the manufacturing process before use. Alternatively, the separation membrane module may be temporarily stopped during use in the manufacturing process and then inspected.

[0145] The technology of the present invention enables efficient testing and confirmation of the performance of separation membrane modules in the production of optical fibers, semiconductors, and electrical products. Various gases can be separated and produced in at least one process selected from natural gas, city gas, biogas, gases containing unreacted raw materials and by-products after reactions such as methanation, gases from fermentation and enzymatic reaction processes, and gases generated from water electrolysis devices. [Example]

[0146] The present invention will be described in more detail below with reference to examples, in which the separation membrane module is of a spiral type, but the present invention is not limited to these examples.

[0147] A. Device mechanism 1 and 2 are schematic diagrams showing an example of an inspection device for a gas separation membrane module of the present invention.

[0148] A gas consisting of one or more types of gas is supplied to the separation membrane module 100 by the gas supply means 101. In the separation membrane module 100, some of the gas permeates through the separation membrane of the separation membrane module and is vented to the permeate gas discharge means 102B, while the other gas is vented to the non-permeate gas discharge means 102C of the separation membrane module. At this time, the non-permeate side of the separation membrane module 100 is sealed by closing the valve 12C. The permeation side of the separation membrane module 100 may be depressurized by a vacuum pump, which acts as a driving force for the gas to permeate through the membrane. The gas permeation rate in the separation membrane module 100 can be adjusted by the degree of vacuum applied by the vacuum pump.

[0149] B. Fabrication of Gas Separation Membranes Unless otherwise specified below, the temperature conditions are room temperature (25°C).

[0150] (gas separation membrane) Nonwoven fabric made of polyester fiber produced by papermaking method (air permeability 1.0cc / cm 2 A 18% by mass solution of polysulfone in dimethylformamide (DMF) was cast onto the nonwoven fabric substrate (1000 nm / sec) at room temperature (25°C) to a coating thickness of 190 μm, and then the substrate was immediately immersed in pure water for 5 minutes to form a porous support layer on the nonwoven fabric substrate.

[0151] Next, the substrate with the porous support layer formed thereon was immersed in an aqueous solution containing 4.0% by mass of m-phenylenediamine for 1 minute, and then nitrogen was sprayed from an air nozzle to remove excess aqueous solution. Subsequently, an n-undecane solution containing 0.2% by mass of trimesic acid chloride heated to 45°C was uniformly applied to the surface of the porous support and dried in an oven at 100°C for 60 seconds. After that, it was left in an air atmosphere for 1 minute to obtain a separation functional layer (polyamide membrane). The obtained separation membrane was held vertically to drain the liquid and washed with pure water at 60°C for 2 minutes to obtain gas separation membrane A.

[0152] C. Separation membrane module (Separation membrane module J) Gas separation membrane A was cut to a width of 300 mm, air-dried in a greenhouse at 25°C, and then folded in two. A non-permeation side channel material (Diomesh PET-Screen 100-55PT (manufactured by Innovex)) was sandwiched between the folded separation membrane. A permeation side channel material (Diomesh PET-Screen 100-55PT (manufactured by Innovex)) was placed on the permeation side of the gas separation membrane, and adhesive was applied to the three edge sides of the permeation side channel material. The laminate (effective membrane area 1.0 m) was then formed. 2 ) was spirally wound around an ABS resin water collection pipe (length: 300 mm, diameter: 17 mm, 80 holes arranged in a straight line on the wall in two rows) to prepare separation membrane module J with a diameter of 2.5 inches.

[0153] (Separation membrane module K) Gas separation membrane A was cut to a width of 300 mm, air-dried in a greenhouse at 25°C, and then folded in two. A feed-side channel material (Diomesh PET-Screen 100-55PT (manufactured by Innovex)) was sandwiched between the folded separation membrane. A permeation-side channel material (Diomesh PET-Screen 100-55PT (manufactured by Innovex)) was placed on the permeation side of the gas separation membrane, and adhesive was applied to the three edge sides of the permeation-side channel material. The laminate (effective membrane area 1.0 m) was then formed. 2 ) was spirally wound around an ABS resin water collection pipe (length: 300 mm, diameter: 17 mm, 80 holes arranged in a straight line on the wall in two rows) to prepare a separation membrane module K with a diameter of 2.5 inches.

[0154] When applying the adhesive, a portion of about 1 cm long where no adhesive was applied was provided near the center of both ends in the length direction of the permeate side channel material.

[0155] (Separation membrane module L) Gas separation composite membrane A was cut to a width of 300 mm, and 5 ml of an aqueous solution prepared by adding 100 ppm sodium hypochlorite to pure water and adjusting the pH to 7 was dropped onto the widthwise center of the separation membrane sheet. After 1 hour, the membrane was washed with pure water and air-dried in a greenhouse at 25°C. The membrane was then folded in half, and a feed-side channel material (Diomesh PET-Screen 100-55PT (manufactured by Innovex)) was sandwiched between the folded membrane. A permeation-side channel material (Diomesh PET-Screen 100-55PT (manufactured by Innovex)) was placed on the permeation side of the gas separation membrane, and adhesive was applied to the three edge sides of the permeation-side channel material. The resulting laminate (effective membrane area 1.0 m) was then assembled. 2 ) was spirally wound around an ABS resin water collection pipe (length: 300 mm, diameter: 17 mm, 80 holes arranged in a straight line on the wall in two rows) to prepare a separation membrane module L with a diameter of 2.5 inches.

[0156] Example 1 Using the gas separation membrane module inspection device configured as shown in Figure 1, valves 12A, B, and C were opened and a gas containing 100 mol% oxygen was supplied at 3 L / min for 2 minutes to replace the air in the module with oxygen. The module's replacement was confirmed by checking whether the oxygen concentration at the non-permeate gas outlet was 99% or higher. Valve 12C was then closed, sealing the non-permeate gas outlet.

[0157] Here, the separation membrane module 100 used was the separation membrane module J produced above, and was installed in a pressure vessel (ROPV, R25C1000E, 2514), where the supply gas ventilation side of the central tube 6 was sealed.

[0158] Next, the supply flow rate was changed to 0.5 L / min at a supply pressure of 0.1 MPa, and a vacuum pump (diaphragm type, N810.3FT.18(EX) manufactured by KNF) was connected to the permeation side of separation membrane module J to reduce the pressure. The pressure was measured to be 10 kPa. A portion of the gas permeated through the separation membrane of separation membrane module J and was vented to permeated gas discharge means 102B.

[0159] The permeated gas discharged from the pressure vessel 7 was measured using a soap film flowmeter (HORIBA, SF-U / VP-2, 3, 4) and found to be 305 mL / min. The amount of gas used in the test was 8 L.

[0160] Example 2 The test was carried out in the same manner as in Example 1, except that the permeated gas was collected from the inside of the separation membrane module J.

[0161] To collect the permeate gas at each site inside the separation membrane module J, a silicone tube (outer diameter 5 mm, inner diameter 3 mm) was inserted from the permeate gas outlet side of the central tube 6. To collect all of the permeate gas vented from the upstream of the central tube 6, a silicone sheet molded to seal the inner diameter (10 mm) of the central tube 6 was attached around the silicone tube near the end of the inserted silicone tube.

[0162] The end of the silicon tube was moved to a point 6 cm from the innermost end of the central tube 6, from the permeation gas outlet side of the central tube 6, and permeation gas sampling began. Thereafter, the end of the silicon tube was moved every 3 cm toward the end of the central tube 6, and permeation gas sampling was continued. Permeation gas sampling ended at a point 6 cm from the permeation gas outlet side of the central tube 6.

[0163] Here, the point 6 cm from the permeate gas outlet side of the central tube 6 was the end of the separation membrane 1 wrapped around the periphery of the central tube 6 .

[0164] The flow rate of the permeated gas sampled at each point was measured using a soap film flow meter (HORIBA, SF-U / VP-2, 3, 4).

[0165] The results of measuring the flow rate of the permeating gas at each point are shown in Table 1. There were no points where the flow rate significantly decreased or increased. The amount of gas used in the test was 9 L.

[0166] [Table 1]

[0167] Example 3 The inspection was carried out in the same manner as in Example 1, except that separation membrane module K was used. Table 1 shows the flow rate measurement results for the permeate gas discharged from the pressure vessel 7. Since the permeation flow rate of the permeate gas increased compared to Example 1, a defect in separation membrane module K could be detected. Furthermore, the amount of gas used in the inspection was 8 L, and the defect could be detected in one inspection.

[0168] Example 4 The inspection was carried out in the same manner as in Example 1, except that separation membrane module L was used. The permeate gas discharged from pressure vessel 7 was 268 mL / min. The permeate flow rate of the permeate gas increased compared to Example 1, and defects in separation membrane module L could be detected. Furthermore, the amount of gas used in the inspection was 8 L, and defects could be detected in one inspection.

[0169] Example 5 The test was carried out in the same manner as in Example 2, except that the separation membrane module used was separation membrane module K and the permeated gas was collected from one location inside separation membrane module K.

[0170] The end of a silicone tube was inserted 15 cm from the innermost end of the central tube 6 at the permeation gas outlet side of the central tube 6, and the permeation gas was sampled. The flow rate of the sampled permeation gas was measured using a soap film flow meter (HORIBA, SF-U / VP-2, 3, 4).

[0171] At the 15 cm point, the permeation flow rate of the permeate gas increased compared to Example 2, and therefore it was possible to detect a defect in the separation membrane module K at a point 15 cm from the end of the innermost central tube 6 from the permeate gas outlet side of the central tube 6. The amount of gas used in the inspection was 8 L, and the defect was detected in a single inspection.

[0172] Example 6 The inspection was carried out in the same manner as in Example 2, except that separation membrane module K was used. The results of measuring the flow rate of the permeated gas at each point are shown in Table 1. The permeation flow rate was significantly higher than in Example 2 at a point 6 cm from the back end of the central tube 6 and at a point 6 cm from the end of the central tube 6. It was estimated that there were abnormalities at both ends of the width of separation membrane module K. As mentioned above, there were some areas in separation membrane module K where adhesive was not applied, which raised concerns about poor adhesion, but this was detected using the method of the present invention. Furthermore, the amount of gas used in the inspection was 9 L, and the defect was detected in a single inspection.

[0173] Example 7 The inspection was carried out in the same manner as in Example 2, except that separation membrane module L was used. The results of measuring the flow rate of the permeated gas at each point are shown in Table 1. The permeation flow rate increased significantly compared to Example 2, particularly at a point 15 cm from the back end of the central tube 6. An abnormality was presumed to exist near the center in the width direction of separation membrane module L. As mentioned above, there was concern that the separation membrane in the center in the width direction of separation membrane module L might have deteriorated in performance due to contact with the sodium hypochlorite aqueous solution, but this was detected using the method of the present invention. Furthermore, the amount of gas used in the inspection was 9 L, and the defect was detected in a single inspection.

[0174] Example 8 In the inspection of Example 7, it was estimated that there was an abnormality near the center in the width direction of the separation membrane module L, so after the inspection of Example 7, an inspection was conducted further near the center. The results of measuring the flow rate of the permeated gas at each point are shown in Table 2. In Example 7, it was estimated that there was an abnormality near the center in the width direction, but from Table 2 it was estimated that there was an abnormality in a position 14 cm to 15 cm from the back side of the end of the central tube 6. The inspection was conducted twice, including the inspection of Example 7, and the total amount of gas used was 17 L.

[0175] [Table 2]

[0176] Example 9 The separation membrane module 100 shown in FIG. 1 was constructed by using the separation membrane module J fabricated above and installed in a pressure vessel (ROPV, R25C1000E, 2514). The supply gas ventilation side of the central tube 6 was sealed. Using the gas separation membrane module inspection device configured as shown in FIG. 1, valves 12A and 12C were closed and valve 12B was opened, and the permeation side of separation membrane module J was connected to a vacuum pump (diaphragm type, N810.3FT.18(EX) manufactured by KNF) to reduce the pressure. The pressure was measured to be 3 kPa.

[0177] Valve 12B was then closed, sealing the permeate gas outlet. Next, valves 12A and 12C were opened, and air was supplied at 1.0 L / min for 1 minute at a supply pressure of 0.1 MPa. Because some of the gas permeates the separation membrane of separation membrane module J, the permeation side pressure gradually increases as the permeation volume increases. Using the permeation side pressure 1 minute after the start of supply as the reference, it took 70 seconds for the permeation side pressure to increase by a further 5 kPa. The amount of gas used in the test was 2.2 L.

[0178] Example 10 The test was carried out in the same manner as in Example 9, except that separation membrane module L was used. The time required for the permeation side pressure to increase by 5 kPa was 56 seconds. It was confirmed that the permeation side pressure increased more quickly than in Example 9. If there was a defect, the amount of gas permeating would increase, so it was possible to detect a defect in the separation membrane module L. The amount of gas used in the test was 1.9 L, and it was possible to confirm that there was a defect in the separation membrane module L while limiting the amount of gas used.

[0179] (Comparative Example 1) The inspection was carried out in the same manner as in Example 3, except that the non-permeation side was not sealed and a gas containing 100 mol % oxygen was supplied at 3 L / min. The flow rate measurement results for the permeation gas discharged from the pressure vessel 7 are shown in Table 1. Since the permeation flow rate was increased compared to Example 1, a defect in the separation membrane module K could be detected.

[0180] On the other hand, the amount of gas used in the test was 32 L, which was four times the amount used in Example 3.

[0181] (Comparative Example 2) The gas was sealed inside the module and the test was carried out. Using the gas separation membrane module test equipment configured as shown in Figure 1, a gas containing 100 mol% oxygen was supplied at 3 L / min for 2 minutes, and the inside of the module was replaced with the sealed gas. The air inside the module was replaced with oxygen. The success of the replacement in the module was confirmed by checking that the oxygen concentration at the non-permeate gas outlet was 99% or higher. Valves 12A, B, and C were then closed, and the supplied gas was sealed inside the module. The sealing pressure was adjusted to 100 kPa.

[0182] Here, the separation membrane module 100 used was the separation membrane module L produced above, and was installed in a pressure vessel (ROPV, R25C1000E, 2514), where the sealing gas ventilation side of the central tube 6 was sealed.

[0183] Next, the valve 12B was opened, and the pressure on the permeation side of the separation membrane module J was reduced by connecting a vacuum pump (diaphragm type, N810.3FT.18(EX) manufactured by KNF).

[0184] The sampling of the permeated gas and the measurement of the flow rate were carried out at each site inside the separation membrane module, as in Example 2. During the operation, the sealed gas decreased, making it difficult to continue the test, so the gas sealing work was carried out again, and the test was continued from the untreated site.

[0185] The results of measuring the flow rate of the permeate gas at each point are shown in Table 1. The permeate flow rate significantly increased compared to Example 2, particularly at the 15 cm point from the rear end of the central tube 6. An abnormality was estimated to exist near the center of the width of the separation membrane module L. As described above, there was concern that the separation membrane in the center of the width of the separation membrane module L might have deteriorated in performance due to contact with the sodium hypochlorite aqueous solution, but this was detected using the method of the present invention. Furthermore, since two 4-L inspections were performed, the amount of gas used was 8 L. A single inspection was not able to detect the defect, so two inspections were required. Furthermore, two inspections were performed similarly to Example 8, and although an abnormality was found near the 15 cm point, the defect was not detected in the first inspection, unlike Example 8. Furthermore, even after two inspections, the abnormality in the 14-15 cm region could not be detected. [Industrial Applicability]

[0186] The gas separation membrane module inspection device of the present invention is an inspection device that supplies gas into a gas separation membrane module, discharges it from the permeation side, and measures the characteristics of the gas that permeates the gas separation membrane module.It can provide an inspection device that uses a small amount of gas to identify the location of abnormalities such as deterioration, damage, and leaks in the gas separation membrane module, and to confirm the degree of deterioration, etc. [Explanation of symbols]

[0187] 1 Separation membrane 2 Non-permeable channel material 3 Permeate side channel material 6 central canal 7. Pressure Vessels 11 Gas sampling tube 12 valves 13 Flow meter 14 Oxygen concentration meter 15 Gas vent pipe 16 Gas Chromatography 17 Conductivity sensor 18 water 100 Separation membrane module 101 Gas sealing means 102 Non-permeate gas and permeate gas exhaust means 103 Apparatus for measuring the properties of non-permeating and permeating gases 201 Supply gas 202 Permeable Gas 203 Non-permeable gas 204 Sampling Gas

Claims

1. The gas supplied to the gas separation membrane module is composed of one or more types of gases, After sealing either the non-permeate outlet or the permeate outlet, while continuously supplying gas to the gas separation membrane module, the non-permeate gas or the permeate gas is continuously discharged from the gas separation membrane module by at least one of pressurizing the supply side and depressurizing the permeate side, and the properties of at least one of the non-permeate gas and the permeate gas of the gas separation membrane module are measured. A method for inspecting a gas separation membrane module.

2. The gas supplied to the gas separation membrane module is composed of one or more types of gases, After sealing one of the non-permeate outlet and the permeate outlet, while continuously supplying gas to the gas separation membrane module, the non-permeate gas or the permeate gas is continuously discharged from the gas separation membrane module by at least one of pressurizing the supply side and depressurizing the permeate side, and the properties of at least one of the non-permeate gas and the permeate gas of the gas separation membrane module are measured at a location within the gas separation membrane module. A method for inspecting a gas separation membrane module.

3. measuring the characteristics of at least one of the non-permeating gas and the permeating gas at two or more locations in the gas separation membrane module; The method for inspecting a gas separation membrane module according to claim 2 .

4. 3. The method for inspecting a gas separation membrane module according to claim 1, wherein the gas separation membrane is a flat membrane.

5. a gas separation membrane module in which the gas separation membrane, the non-permeation side flow path material, and the permeation side flow path material are wound around a central tube that collects the permeated gas of the gas separation membrane; 3. A method for inspecting a gas separation membrane module according to claim 1 or 2.

6. The supply gas is composed of one type of gas.

3. A method for inspecting a gas separation membrane module according to claim 1 or 2.

7. measuring one or more characteristics of the non-permeating gas and / or the permeating gas, such as volume flow rate, mass flow rate, composition, temperature, pressure, and thermal conductivity; 3. A method for inspecting a gas separation membrane module according to claim 1 or 2.

8. The gas separation membrane module has a means for supplying a gas composed of one or more types of gases to the gas separation membrane module, a gas separation membrane module for separating the supplied gas into a non-permeate gas and a permeate gas, at least one of a means for pressurizing the non-permeate side and a means for depressurizing the permeate side, a means for discharging the non-permeate gas or the permeate gas from the gas separation membrane module, and a means for measuring the properties of at least one of the non-permeate gas and the permeate gas from the gas separation membrane module. Gas separation membrane module inspection equipment.

9. 2. The inspection method for a gas separation membrane module according to claim 1, wherein the inspection method is used in at least one process selected from the group consisting of gas separation in the manufacturing processes of optical fibers, semiconductors, and electrical appliances, separation of gases produced by reactions of natural gas, city gas, biogas, and methanation, separation of gases containing unreacted raw materials and by-products, separation of gases produced from water electrolysis equipment, and separation of gases for concentrating a target gas from a mixed gas.

10. A method for manufacturing an optical fiber, comprising using the method for inspecting a gas separation membrane module according to claim 1.

11. A method for manufacturing a semiconductor, comprising using the method for inspecting a gas separation membrane module according to claim 1.

12. A method for manufacturing an electrical product, comprising using the method for inspecting a gas separation membrane module according to claim 1.

13. A gas production method, characterized by using the gas separation membrane module inspection method of claim 1, for separating at least one gas selected from natural gas, city gas, biogas, gases produced by methanation reactions, gases containing unreacted raw materials or by-products, gases from fermentation or enzymatic reaction processes, and gases generated from water electrolysis devices.

14. An optical fiber produced using a gas separation membrane module whose performance has been tested by the method of claim 1.

15. A semiconductor manufactured using a gas separation membrane module whose performance has been tested by the method of claim 1.

16. An electrical product manufactured using a gas separation membrane module whose performance has been tested by the method of claim 1.

17. A gas separation device that uses a gas separation membrane module whose performance has been tested by the method of claim 1, and separates at least one gas selected from natural gas, city gas, biogas, gases produced by methanation reactions, gases containing unreacted raw materials or by-products, gases produced in fermentation or enzymatic reaction processes, and gases generated from water electrolysis devices.

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