Gas supply device and gas supply method

Abstract

To provide an efficient gas supply device and gas supply method. [Solution] The supply device 100 comprises a gas separation membrane 1 that is permeable to the product gas, a gas separation container 2 that houses the separation membrane 1, and a heating device 20 that heats the separation membrane 1. The gas separation container 2 has a first space 31 that stores a raw solution of the product gas, a second space 32 that is partitioned by the first space 31 and the separation membrane 1, a carrier gas inlet 42 that communicates with the second space 32 and introduces a carrier gas into the second space 32, and a discharge outlet 44 that communicates with the second space 32 and discharges a mixed gas of the carrier gas and the product gas from the second space 32.

Description

[Technical Field]

[0001] The present invention relates to a gas supply device and a gas supply method. [Background technology]

[0002] The increasing integration of semiconductors necessitates lower temperatures and improved throughput in semiconductor manufacturing processes. To achieve this throughput improvement, highly reactive gases such as hydrogen peroxide and hydrazine are required as semiconductor material gases. However, these highly reactive gases are prone to decomposition during transportation and storage. Therefore, to prevent decomposition during transportation and storage, these highly reactive gases are sometimes transported and stored in the form of a solution in which the gas is dissolved in water or an organic solvent. For example, hydrogen peroxide is sometimes transported and stored in the form of an aqueous solution, and hydrazine is sometimes transported and stored in the form of a mixture (solution) with an organic solvent.

[0003] When a highly reactive gas is in a solution state as described above, it is necessary to separate the highly reactive gas from the solution before using it. However, when a highly reactive gas is separated from such a solution and used, problems arise such as a decrease in the concentration of the gas or contamination with solvent vapor. For this reason, as disclosed in Patent Document 1, for example, a concentrated gas with an increased concentration is obtained using a separation membrane, and this concentrated gas is sometimes supplied to a device that uses the gas.

[0004] Patent Document 1 discloses a supply method and supply device for supplying gaseous materials (product gases) used, for example, in the manufacture of semiconductor devices. This supply method includes a mixed gas preparation step in which a carrier gas is introduced into a container containing the material in solid or liquid form to obtain a mixed gas of the vaporized material and the carrier gas; a concentration step in which a separation membrane is used to obtain a concentrated gas by increasing the concentration of the material in the mixed gas; and a supply step in which the concentrated gas is supplied to an apparatus that uses the material. In this supply method, the carrier gas in the mixed gas permeates the separation membrane, increasing the concentration of the material in the supplied mixed gas and turning it into a concentrated gas. Patent Document 1 discloses that high concentrations are required for gaseous materials used, for example, in the manufacture of semiconductor devices. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2024-118353 Summary of the Invention [Problem to be solved by the invention]

[0006] In the supply method and supply device disclosed in Patent Document 1, as described above, a carrier gas is introduced into a container containing a gaseous material (hereinafter referred to as product gas) to be used in a downstream process in a solid or liquid state, and a mixture of the vaporized product gas and the carrier gas is obtained. The concentration of the product gas contained in this mixture is then increased using a separation membrane. For example, the vaporization rate of the product gas from its solid or liquid state is limited, limiting the amount of product gas that can be supplied, making it difficult to efficiently supply a high-concentration product gas. Furthermore, further concentrating the product gas after obtaining the mixture can complicate the process, making it difficult to efficiently supply a high-concentration product gas. Given these circumstances, there is a demand for greater efficiency in gas supply devices and gas supply methods for highly reactive gases.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an efficient gas supply device and gas supply method. [Means for solving the problem]

[0008] In order to achieve the above object, the gas supply device according to the present invention comprises: a gas separation membrane that allows the product gas to permeate; a gas separation vessel containing the separation membrane; a heating device that heats the separation membrane, The gas separation vessel comprises: a first space portion for storing a raw material solution of the product gas; a second space portion partitioned by the first space portion and the separation membrane; a carrier gas inlet port communicating with the second space portion and introducing a carrier gas into the second space portion; The gas supply system has a delivery port that communicates with the second space and delivers the mixed gas of the carrier gas and the product gas from the second space.

[0009] In order to achieve the above object, a gas supply method according to the present invention comprises: a separation step of contacting a raw solution of the product gas with a gas separation membrane and separating the product gas from the raw solution by permeating the separation membrane; a heating step of heating the separation membrane; a delivery step of introducing a carrier gas into the product gas separated in the separation step and delivering a mixed gas of the product gas and the carrier gas, The heating step is carried out during the separation step. [Effects of the Invention]

[0010] According to the present disclosure, an efficient gas supply device and gas supply method can be provided. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is an explanatory diagram of a configuration of a gas supply device (supply device) according to an embodiment of the present invention. [Figure 2] FIG. 10 is an explanatory diagram of the configuration of a gas supply device (supply device) according to another embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0012] A gas supply apparatus and a gas supply method according to an embodiment of the present invention will be described with reference to the drawings.

[0013] First, an outline of the gas supply device and gas supply method according to this embodiment will be described.

[0014] FIG. 1 shows an explanatory diagram of the configuration of a supply device 100, which is an example of a gas supply device according to this embodiment.

[0015] 1, the supply device 100 includes a gas separation membrane 1 that is permeable to the product gas, a gas separation vessel 2 that houses the separation membrane 1, and a heating device 20 that heats the separation membrane 1. The gas separation vessel 2 has a first space 31 that stores a raw solution of the product gas, a second space 32 that is partitioned by the first space 31 and the separation membrane 1, a carrier gas inlet 42 that communicates with the second space 32 and introduces a carrier gas into the second space 32, and an outlet 44 that communicates with the second space 32 and delivers a mixed gas of the carrier gas and the product gas from the second space 32.

[0016] The gas supply method according to this embodiment includes a separation step in which a raw solution of a product gas is brought into contact with a gas separation membrane 1 and the product gas is separated from the raw solution by passing through the separation membrane 1, a heating step in which separation membrane 1 is heated, and a delivery step in which a carrier gas is introduced into the product gas separated in the separation step and a mixed gas of the product gas and carrier gas is delivered. The heating step is carried out during the separation step.

[0017] The supply device 100 can efficiently supply a gas (mixed gas) containing a product gas. Specifically, the supply device 100 can efficiently separate the product gas from the raw material solution of the product gas, thereby efficiently supplying the mixed gas.

[0018] Furthermore, according to the gas supply method of this embodiment, a gas (mixed gas) containing a product gas can be efficiently supplied. The gas supply method of this embodiment can be realized by, for example, a supply device 100.

[0019] The supply device 100 will be described in detail below. The gas supply method according to this embodiment will be described in detail using the supply device 100 as an example.

[0020] The supply device 100 separates a product gas at a high concentration (i.e., with as little solvent component of the raw material solution as possible) from a raw material solution of the product gas supplied from an upstream device or the like, and supplies the mixed gas of this product gas and carrier gas to a downstream device or the like (e.g., semiconductor manufacturing equipment). In this embodiment, the raw material solution refers to a solution containing raw material components that are the raw material of the product gas. Also, the inclusion of gas resulting from the solvent of the raw material solution in the mixed gas is permitted. Also, the term "gas" refers to a gaseous state. In this embodiment, the concept of "gas" includes the concept of vapor.

[0021] An example of a product gas is a highly reactive gas. For example, examples of highly reactive gases that are in high demand in semiconductor manufacturing processes, i.e., that are often used in semiconductor manufacturing processes, are gases with highly polar molecular structures (gases with polar molecules), such as hydrazine, hydrogen peroxide, and formic acid.

[0022] Preferred gases as the carrier gas are hydrogen, nitrogen, oxygen, helium, argon, and a mixture of at least two of these gases.

[0023] The raw material solution is a solution containing the components (raw material components) of the product gas. That is, the raw material solution is a solution containing raw material components made of polar molecules as raw materials for the product gas.

[0024] Examples of raw material solutions are as follows: When the product gas is hydrazine, the raw material solution is a solution of liquid hydrazine mixed with an organic solvent (e.g., diglyme (diethylene glycol dimethyl ether)). When the product gas is hydrogen peroxide, the raw material solution is aqueous hydrogen peroxide. When the product gas is formic acid, the raw material solution is an aqueous solution of formic acid.

[0025] The supply device 100 may, for example, include a separation membrane 1, a gas separation container 2, a heating device 20, a liquid level sensor 21, a liquid volume control mechanism 5, a concentration sensor 89, and a pressure control mechanism 6. In addition to the above, the supply device 100 may further include a raw material container 70 such as a storage tank (for example, a cushion tank) that temporarily stores the raw material solution to be supplied to the gas separation container 2.

[0026] Separation membrane 1 is a membranous member that allows the product gas in the raw solution to pass from one side of the membrane to the other side, while preventing or providing very little permeation for the solvent in the raw solution. In other words, separation membrane 1 is a membranous member that can separate (extract) a high concentration of product gas from the raw solution. Hereinafter, the separation of product gas from the raw solution by passing it through separation membrane 1 may be simply referred to as "separating product gas from the raw solution." Use of separation membrane 1 makes it possible to separate product gas from the raw solution while suppressing the intrusion of solvent into the raw solution.

[0027] The type of membrane for separation membrane 1 may be appropriately selected depending on the product gas to be separated and the type of solvent in the raw material solution. Separation membrane 1 is preferably one that does not allow or is extremely impermeable to gases other than the product gas.

[0028] Examples of membranous materials suitable for the separation membrane 1 include zeolite membranes and metal-organic framework membranes (membranes formed from metal-organic framework (MOF)-based materials). These membranes have a particularly high ability to selectively adsorb polar molecules, and are therefore suitable for separating gases with highly polar molecular structures such as hydrazine, hydrogen peroxide, and formic acid. The separation membrane 1 may be a membranous material including at least one of a zeolite membrane and a metal-organic framework membrane.

[0029] Among zeolite membranes, particularly suitable are CHA-type zeolite membranes such as membranes using high-silica CHA-type zeolite with a porous aluminum oxide substrate, for example, ZEBREX (registered trademark) ZX1 and ZX3 manufactured by Mitsubishi Chemical Corporation. The use of membranes using MFI-type zeolite as the zeolite membrane is also not excluded. When a zeolite membrane is used as the separation membrane 1, molecules with a molecular diameter smaller than the pore diameter of the zeolite constituting the zeolite membrane and high polarity are preferentially adsorbed to the zeolite membrane and permeate through the membrane.

[0030] Among the metal-organic structure films, particularly suitable are those containing a CN-bridged complex skeleton in their molecular structure, which has a strong bond between the metal and organic molecules in the internal structure.

[0031] The gas separation vessel 2 is a vessel that houses the separation membrane 1 in its internal space. The shape of the gas separation vessel 2 is not important as long as it has an internal space that can house the separation membrane 1, but the gas separation vessel 2 may be formed into a cylindrical or rectangular parallelepiped shape, for example.

[0032] The internal space of the gas separation vessel 2 is divided by the separation membrane 1 into a first space portion 31 and a second space portion 32 .

[0033] The gas separation vessel 2 may be made of, for example, a metal alloy such as an iron alloy, or a corrosion-resistant resin such as a fluororesin.

[0034] The gas separation container 2 is equipped with a raw solution inlet 41 for introducing the raw solution into the first space 31, an exhaust port 43 for exhausting unnecessary gas from the first space 31 to the outside of the system of the supply device 100, a carrier gas inlet 42 for introducing a carrier gas into the second space 32, and an outlet 44 for delivering a mixed gas of the carrier gas and the product gas from the second space 32. A tip 73a of a drain pipe 73 for discharging the raw solution from the first space 31 is inserted into the first space 31 of the gas separation container 2.

[0035] The first space 31 is a spatial region partitioned by the inner wall of the gas separation vessel 2 and the separation membrane 1, or a spatial region partitioned by the separation membrane 1, for storing the raw solution (solution L2) introduced from the raw solution inlet 41. The first space 31 is partitioned so that the raw solution stored in the first space 31 comes into contact with the separation membrane 1. In other words, the separation membrane 1 is disposed in a position where it comes into contact with the raw solution.

[0036] It is desirable that a gas phase and a liquid phase (raw material solution) exist in the first space portion 31. The gas phase may be nitrogen, air, or a product gas.

[0037] The second space portion 32 is a spatial region separate from the first space portion 31 in the internal space of the gas separation container 2, partitioned by the inner wall of the gas separation container 2 and the separation membrane 1, or partitioned by the separation membrane 1, for receiving the raw material gas that has permeated the separation membrane 1.

[0038] The second space 32 is adjacent to the first space 31 via the separation membrane 1. A raw material gas separated by the separation membrane 1 from the raw material solution stored in the first space 31 flows into the second space 32. The raw material gas that has flowed into the second space 32 interdiffuses with a carrier gas introduced into the second space 32 via a carrier gas inlet 42 (described later) to form a mixed gas. The mixed gas is then delivered to a downstream device in the process via a delivery outlet 44 (described later) (the above is an example of a delivery process).

[0039] In this embodiment, the gas separation container 2 is formed in a cylindrical shape and is disposed with the axis of the cylinder aligned horizontally. The separation membrane 1 is formed as a cylindrical body 10 and is housed in the internal space of the gas separation container 2. The cylindrical body 10 is disposed with the axis of the cylinder aligned horizontally.

[0040] In this embodiment, the second space 32 is a space inside the cylindrical body 10 (separation membrane 1), partitioned by the cylindrical body 10. The first space 31 is the internal space of the gas separation container 2, excluding the second space 32. At least a portion of the cylindrical body 10 is immersed in the raw material solution (solution L2) stored in the second space 32. FIG. 1 illustrates an example in which the entire cylindrical body 10 is immersed in the raw material solution. As a result, the separation membrane 1 is in contact with the raw material solution stored in the second space 32.

[0041] By bringing the raw solution of the product gas into contact with the gas separation membrane 1, the product gas permeates the separation membrane 1, thereby separating (evaporating) the product gas from the raw solution (an example of a separation process). Note that in this embodiment, evaporation of the product gas through the separation membrane 1 is included in the concept of the product gas permeating the separation membrane 1.

[0042] The raw material solution inlet 41 is an inlet for introducing the raw material solution (solution L1) from the raw material container 70 into the first space 31. The raw material solution inlet 41 communicates with the first space 31 a liquid supply pipe 72, which is a pipe for supplying the raw material solution from the raw material container 70 to the first space 31, so that the raw material solution can be introduced from the raw material container 70 and the liquid supply pipe 72 into the first space 31. The raw material container 70 may be successively replenished with the raw material solution via the pipe 71 from a raw material solution preparation tank, for example, located upstream in the process.

[0043] The drain pipe 73 is a pipe that discharges the raw material solution (solution L2) as a waste liquid (solution L3) from the first space 31 to the outside of the system of the supplying device 100. The drain pipe 73 sucks up the raw material solution from a tip 73a on the base end side of the drain pipe 73 that is immersed in the raw material solution (solution L2) stored in the first space 31, and discharges it as a waste liquid to a waste liquid treatment device or the like outside the system of the supplying device 100.

[0044] In the gas separation container 2, the separation membrane 1 separates the raw gas components from the raw solution (solution L2) stored in the first space 31, thereby reducing the raw gas components in the raw solution. For this reason, new raw solution is continuously introduced into the first space 31 through the raw solution inlet 41. The raw solution with the reduced raw gas components is discharged as waste liquid (solution L3) to the outside of the supply device 100 through the drain pipe 73.

[0045] The exhaust port 43 is an outlet for discharging waste gas (gas G3) from the first space 31 to the outside of the supplying device 100 system. In the first space 31, product gas may evaporate from the raw material solution, or solvent components may volatilize. The exhaust port 43 discharges these product gases and solvent gases as waste gas from the first space 31. The exhaust port 43 connects the first space 31 to an exhaust pipe 74, which sends the waste gas to a waste gas treatment device or the like outside the supplying device 100 system. The exhaust port 43 is positioned so that it does not come into contact with the raw material solution stored in the first space 31.

[0046] The carrier gas inlet 42 is an inlet for introducing a carrier gas (gas G1) supplied from, for example, the upstream side of the process into the second space 32. The carrier gas inlet 42 communicates with the second space 32 a carrier gas supply pipe 82, which is a pipe through which the carrier gas is supplied from the upstream side, so that the carrier gas can be introduced from the carrier gas supply pipe 82 into the second space 32. The carrier gas introduced into the second space 32 from the carrier gas inlet 42 interdiffuses with the product gas within the second space 32, forming a mixed gas of the carrier gas and the product gas.

[0047] The outlet 44 is an outlet for delivering the mixed gas (gas G2) from the second space 32 to a device or the like located downstream in the process. The outlet 44 connects the second space 32 to a mixed gas supply pipe 84, which is a pipe for supplying the mixed gas to a device or the like located downstream in the process.

[0048] Ports and pipes such as the raw material solution inlet 41, the carrier gas inlet 42, the exhaust port 43, the delivery port 44, the liquid supply pipe 72, the drain pipe 73, the exhaust pipe 74, the carrier gas supply pipe 82, and the mixed gas supply pipe 84 may be formed from a metal alloy such as an iron alloy, or a corrosion-resistant resin such as a fluororesin.

[0049] In the second space 32, the raw material gas separated from the raw material solution (solution L2) stored in the first space 31 is mixed with the carrier gas introduced from the carrier gas inlet 42, and the mixed gas having the concentration required by the downstream device in the process is sent out from the outlet 44 to the downstream device in the process.

[0050] The heating device 20 is a device equipped with a heating mechanism and a heat source for heating the separation membrane 1 (an example of a heating step). The heating device 20 may heat the separation membrane 1 or the raw material solution (solution L2) stored in the first space portion 31 via the gas separation container 2. In other words, the heating device 20 may heat the gas separation container 2.

[0051] The heating device 20 may be, for example, a device that uses an electric heater or a steam heater as a heating mechanism or heat source. The heating device 20 may also be a device that uses a heating mechanism that utilizes electromagnetic induction or radiant heat transfer.

[0052] The heating device 20 may be installed in the gas separation vessel 2 so as to cover at least a part of the outer surface of the gas separation vessel 2, for example.

[0053] In the supply device 100 of this embodiment, the heating device 20 can heat the gas separation container 2, the separation membrane 1, and the raw solution (solution L2), which allows the product gas in the raw solution to more selectively permeate the separation membrane 1.

[0054] Specifically, heating the separation membrane 1 causes the components of the product gas to be selectively adsorbed onto the separation membrane 1, thereby facilitating selective permeation through the separation membrane 1. The surface diffusion of the product gas components adsorbed onto the separation membrane 1 is promoted, particularly by heating the separation membrane 1, thereby facilitating permeation through the separation membrane 1. The components of the product gas that permeate the separation membrane 1 from the first spatial portion 31 side to the second spatial portion 32 side are desorbed from the separation membrane 1 and are more likely to diffuse into the second spatial portion 32, particularly by heating the separation membrane 1. The promotion of desorption and diffusion of the product gas components on the second spatial portion 32 side of the separation membrane 1 further facilitates selective permeation of the product gas through the separation membrane 1. Thus, by performing a heating step during the separation step, the efficiency of separation of the product gas from the raw solution is improved.

[0055] A specific example of the effect of the heating process is as follows. For example, when a zeolite membrane is used as the separation membrane 1, molecules with a molecular diameter smaller than the pore diameter of the zeolite and high polarity (molecules of product gas components) are preferentially adsorbed to the separation membrane 1 (zeolite) over other molecules. At this time, heating the separation membrane 1 can promote the adsorption, desorption, and surface diffusion of these molecules, allowing the product gas to be selectively separated. For example, when a mixed solution of hydrazine and an organic solvent is used as a raw material solution and is brought into contact with a CHA-type zeolite membrane as the separation membrane 1, hydrazine molecules smaller than the pore diameter of the zeolite (0.38 nm to 0.40 nm) are selectively adsorbed to the separation membrane 1 (preferentially over organic solvent molecules). Under heating conditions in which the separation membrane 1 is heated, hydrazine repeatedly adsorbs and desorbs within the separation membrane 1, allowing the hydrazine to permeate the separation membrane 1. In this way, hydrazine can be selectively separated (evaporated) from the mixed solution.

[0056] Furthermore, for example, when a mixed solution of formic acid and an organic solvent is used as a raw material solution and is brought into contact with an MFI zeolite membrane as the separation membrane 1, formic acid molecules that are smaller than the pore size of the MFI zeolite are selectively adsorbed onto the separation membrane 1. As in the case of hydrazine described above, under heating conditions in which the separation membrane 1 is heated, formic acid can be selectively separated (evaporated).

[0057] It should be noted that when a zeolite membrane is used as the separation membrane 1 of the supply device 100, the raw material gases that can be selectively separated (evaporated) are not limited to these exemplified hydrazine and formic acid.

[0058] The heating device 20 heats the gas separation container 2 to, for example, 30°C or higher and 200°C or lower, preferably 30°C or higher and 150°C or lower. That is, the heating device 20 heats the separation membrane 1 to 30°C or higher and 200°C or lower, preferably 30°C or higher and 150°C or lower. By keeping the temperature of the separation membrane 1 within the range of 30°C or higher and 200°C or lower, the product gas is efficiently separated from the raw solution. By keeping the temperature of the separation membrane 1 within the range of 30°C or higher and 150°C or lower, the product gas may be separated even more efficiently from the raw solution.

[0059] The heating device 20 may be controlled to change the amount of heat applied to the gas separation vessel 2, the separation membrane 1, or the first space 31, for example, to maintain a constant temperature or to reach a predetermined target temperature. In this case, temperature sensors for measuring the temperatures of the gas separation vessel 2, the separation membrane 1, or the first space 31 may be attached to these, and the amount of heat applied by the heating device 20 may be controlled based on the measurement results of these temperature sensors. For example, a temperature sensor 29 for measuring the temperature of the separation membrane 1 may be attached to the separation membrane 1, and the amount of heat applied to the gas separation vessel 2 by the heating device 20 may be controlled based on the temperature of the separation membrane 1 measured by this temperature sensor 29.

[0060] The temperature of the separation membrane 1 may be determined by measuring the temperature of the raw material solution (solution L2) stored in the first space 31. For example, the temperature of the raw material solution stored in the first space 31 may be regarded as the temperature of the separation membrane 1. Specifically, in order to measure the temperature of the separation membrane 1, a temperature sensor may be provided in the gas separation container 2, inserted into the space of the first space 31 at a position where it comes into contact with the raw material solution stored in the first space 31.

[0061] The amount of heat generated by the heating device 20 may be controlled based on the result of detection of the concentration of the product gas contained in the mixed gas by a concentration sensor 89, which will be described later.

[0062] As an example of a case where a relationship holds that as the temperature of separation membrane 1 increases within a certain temperature range, the product gas becomes more likely to selectively permeate separation membrane 1, and as the temperature of separation membrane 1 decreases, the product gas becomes less likely to permeate separation membrane 1, heating device 20 may control the amount of heating as follows.

[0063] For example, if the concentration of the product gas contained in the mixed gas is higher than the target value, the heating device 20 may reduce the amount of heat to lower the temperature of the gas separation vessel 2, the separation membrane 1, or the first space 31. Alternatively, if the concentration of the product gas contained in the mixed gas is lower than the target value, the heating device 20 may increase the amount of heat to raise the temperature of the gas separation vessel 2, the separation membrane 1, or the first space 31. The amount of heat may be controlled so that the concentration of the product gas contained in the mixed gas remains constant.

[0064] That is, the amount of heat may be controlled based on the temperature of the gas separation vessel 2, the separation membrane 1, or the first space portion 31, and the concentration of the product gas contained in the mixed gas. For example, the temperature of the separation membrane 1 may be set within a range of 30°C or higher and 150°C or lower, and the amount of heat may be controlled based on the detection result of the concentration of the product gas contained in the mixed gas.

[0065] The liquid level sensor 21 is a detection device that detects the liquid level of the raw solution (solution L2) stored in the first space portion 31. The liquid level sensor 21 may be of any type as long as it can detect the liquid level of the raw solution (solution L2). As examples of the liquid level sensor 21, an ultrasonic level sensor that detects the liquid level position using ultrasonic waves, a laser level sensor that detects the liquid level position using a laser, or a float level sensor that detects the liquid level position using a float can be used. The liquid level sensor 21 may be installed at an appropriate position in the gas separation vessel 2 depending on the liquid level detection method.

[0066] The liquid volume control mechanism 5 is a mechanism that controls the liquid level of the raw material solution (solution L2) stored in the first space portion 31 based on the detection result of the liquid level of the raw material solution by the liquid level sensor 21. The liquid volume control mechanism 5 may include a supply / discharge mechanism that supplies the raw material solution to the first space portion 31 or discharges the raw material solution from the first space portion 31.

[0067] The liquid level of the raw solution contacting the separation membrane 1 can be controlled (adjusted) by controlling the liquid level of the raw solution by the liquid volume control mechanism 5. By controlling the liquid volume control mechanism 5, for example, the liquid level of the raw solution contacting the separation membrane 1 can be kept constant.

[0068] Controlling the liquid level of the raw solution in contact with the separation membrane 1 may make it possible to adjust the rate of permeation of the product gas through the separation membrane 1. For example, controlling the liquid level of the raw solution in contact with the separation membrane 1 may make it possible to maintain a constant rate of permeation of the product gas through the separation membrane 1. Maintaining a constant rate of permeation of the product gas through the separation membrane 1 makes it easier to maintain a constant concentration of the product gas contained in the mixed gas.

[0069] In this embodiment, the liquid volume control mechanism 5 may include, as a supply / discharge mechanism, a liquid delivery mechanism 51 that is installed in the raw material container 70, piping 71, drain pipe 73, and liquid supply pipe 72 and that delivers the raw material solution (solution L1) from the raw material container 70 to the first space 31, and a liquid delivery mechanism 52 that is installed in the drain pipe 73 and that discharges the raw material solution (solution L2) from the first space 31 to the outside of the system as waste liquid (solution L3).

[0070] An example of the liquid sending mechanism 51 is a liquid sending pump or a flow rate control valve.

[0071] An example of the liquid sending mechanism 52 is a liquid sending pump or a flow rate control valve.

[0072] The liquid volume control mechanism 5 controls the operation (e.g., liquid volume, liquid output, valve opening) of the liquid delivery mechanisms 51 and 52 as supply and discharge mechanisms based on the detection results of the liquid level of the raw solution (solution L2) by the liquid level sensor 21, and can control the liquid level of this raw solution (e.g., keep the liquid level constant).

[0073] The liquid volume control mechanism 5 may also control the residence time of the raw material solution (solution L2) stored in the first space 31. This residence time control may be performed by controlling the supply and discharge mechanism, similar to the control of the liquid level of the raw material solution performed by the liquid volume control mechanism 5 described above. By controlling this residence time, the concentration of the product gas component in the raw material solution stored in the first space 31 can be adjusted (for example, kept constant).

[0074] When the supply device 100 is supplying the mixed gas, the concentration of the product gas in the raw solution (solution L2) stored in the first spatial portion 31 is lower than the concentration of the product gas in the raw solution (solution L1) supplied from the raw material container 70. If the concentration of the product gas components in the raw solution is low, the rate of permeation of the product gas through the separation membrane 1 will be slow. If the concentration of the product gas components in the raw solution is high, the rate of permeation of the product gas through the separation membrane 1 will be fast. Therefore, the liquid volume control mechanism 5 can adjust the concentration of the product gas components in the raw solution and thereby adjust the rate of permeation of the product gas through the separation membrane 1 by controlling the residence time of the raw solution (solution L2) stored in the first spatial portion 31.

[0075] The concentration sensor 89 is a device that measures the concentration of the product gas contained in the mixed gas (gas G2). The concentration sensor 89 may be selected appropriately depending on the type of product gas, and any type may be used as long as it can measure the concentration of the product gas contained in the mixed gas. For example, the concentration sensor 89 may be an optical gas concentration meter that uses ultraviolet light (e.g., vacuum ultraviolet light) or infrared light, or an ultrasonic gas concentration meter.

[0076] The concentration sensor 89 may be installed in the mixed gas supply pipe 84, for example, and may measure the concentration of the product gas contained in the mixed gas flowing through the mixed gas supply pipe 84.

[0077] The pressure control mechanism 6 is a mechanism that controls the pressure of the mixed gas in the second space portion 32 based on the detection result of the concentration of the product gas contained in the mixed gas by the concentration sensor 89. The pressure control mechanism 6 may include a delivery amount control mechanism that controls the flow rate of the mixed gas (gas G2) delivered from the delivery port 44.

[0078] The pressure control mechanism 6 controls the pressure of the mixed gas in the second spatial portion 32, thereby controlling (adjusting) the pressure difference (hereinafter referred to as the pressure difference in the separation membrane 1) between the pressure in the space on the first spatial portion 31 side (the pressure of the raw material solution) and the pressure in the space on the second spatial portion 32 side (the pressure of the mixed gas) in the separation membrane 1. Control by the pressure control mechanism 6 makes it possible to keep the pressure difference in the separation membrane 1 constant, for example.

[0079] Controlling the pressure difference across the separation membrane 1 may make it possible to adjust the rate at which the product gas permeates through the separation membrane 1. For example, controlling the pressure difference across the separation membrane 1 may make it possible to maintain a constant rate at which the product gas permeates through the separation membrane 1. Maintaining a constant rate at which the product gas permeates through the separation membrane 1 makes it easier to maintain a constant concentration of the product gas contained in the mixed gas.

[0080] If the permeation rate of the product gas through the separation membrane 1 decreases and the concentration of the product gas in the mixed gas becomes lower than the target value, the permeation rate of the product gas through the separation membrane 1 may be increased by having the pressure control mechanism 6 adjust the pressure of the mixed gas in the second space portion 32 so as to increase the pressure difference across the separation membrane 1.

[0081] If the permeation rate of the product gas through the separation membrane 1 becomes too high and the concentration of the product gas in the mixed gas becomes higher than the target value, the permeation rate of the product gas through the separation membrane 1 may be slowed down by the pressure control mechanism 6 adjusting the pressure of the mixed gas in the second space portion 32 so as to reduce the pressure difference across the separation membrane 1.

[0082] The pressure control mechanism 6 controls the pressure of the mixed gas in the second space portion 32 to control the pressure difference in the separation membrane 1, thereby adjusting the rate of permeation of the product gas through the separation membrane 1. The pressure control mechanism 6 also controls the pressure of the mixed gas in the second space portion 32 to adjust the rate of permeation of the product gas through the separation membrane 1, thereby controlling (e.g., keeping constant) the concentration of the product gas contained in the mixed gas (gas G2).

[0083] In this embodiment, the pressure control mechanism 6 may include, as a discharge amount control mechanism, a mixed gas supply pipe 84 and a valve device 61 such as a flow control valve or a pressure control valve that is installed in the mixed gas supply pipe 84 and controls the flow rate of the mixed gas flowing through it.

[0084] The pressure control mechanism 6 can control the pressure of the mixed gas in the second space portion 32 by controlling the flow rate of the mixed gas flowing through the mixed gas supply pipe 84, i.e., by controlling the flow rate of the mixed gas (gas G2) discharged from the discharge port 44.

[0085] The pressure control mechanism 6 controls the operation of the valve device 61 (e.g., the valve opening) based on the detection results of the concentration of the product gas contained in the mixed gas by the concentration sensor 89, thereby controlling the flow rate of the mixed gas (gas G2) discharged from the discharge port 44 and controlling the pressure of the mixed gas in the second space portion 32.

[0086] The valve device 61 can be controlled to increase the pressure of the mixed gas in the second space portion 32, for example, by increasing the valve opening degree. The valve device 61 can be controlled to decrease the pressure of the mixed gas in the second space portion 32, for example, by decreasing the valve opening degree.

[0087] In this way, an efficient gas supply device and gas supply method can be provided.

[0088] [Another embodiment] (1) In the above embodiment, the separation membrane 1 in the supply device 100 is formed as a cylindrical body 10, and is housed in the internal space of the gas separation container 2, and the cylindrical body 10 is immersed in the raw material solution. Also, the second space portion 32 is a space defined by the cylindrical body 10 (separation membrane 1) within the cylindrical body 10. However, the separation membrane 1 is not limited to being formed in a cylindrical shape.

[0089] 2, the separation membrane 1 may be flat. The second space 32 may be a space region separate from the first space 31 in the internal space of the gas separation container 2, which is partitioned by the inner wall of the gas separation container 2 and the separation membrane 1.

[0090] 2, a flat separation membrane 1 divides the internal space of a gas separation container 2 into a first space 31 disposed above the separation membrane 1 and a second space 32 disposed below the separation membrane 1. The raw material solution stored in the first space 31 is in contact with the upper surface of the separation membrane 1.

[0091] (2) In the above embodiment, it has been described that the liquid volume control mechanism 5 controls the liquid level of the raw material solution stored in the first space portion 31 (for example, keeps the liquid level constant). It has also been described that the liquid volume control mechanism 5 may control the residence time of the raw material solution (solution L2) stored in the first space portion 31.

[0092] The liquid volume control mechanism 5 may control the liquid level of the raw material solution stored in the first space 31 and the residence time of the raw material solution stored in the first space 31, as exemplified above, based on the detection results of the concentration of the product gas contained in the mixed gas by the concentration sensor 89.

[0093] For example, if the concentration of the product gas contained in the mixed gas becomes lower than the target value, the liquid volume control mechanism 5 may perform control such as increasing the liquid level of the raw material solution stored in the first space 31 or shortening the residence time of the raw material solution stored in the first space 31. If the concentration of the product gas contained in the mixed gas becomes higher than the target value, the liquid volume control mechanism 5 may perform control such as decreasing the liquid level of the raw material solution stored in the first space 31 or lengthening the residence time of the raw material solution stored in the first space 31.

[0094] The configurations disclosed in the above embodiments (including other embodiments, the same applies hereinafter) can be applied in combination with configurations disclosed in other embodiments, unless a contradiction arises. Furthermore, the embodiments disclosed in this specification are merely examples, and the present invention is not limited to these, and can be modified as appropriate within the scope of the purpose of the present invention. [Industrial Applicability]

[0095] The present invention can be applied to a gas supply device and a gas supply method. [Explanation of symbols]

[0096] 1: Separation membrane 10: Cylindrical body 100: Feeding device 2: Gas separation vessel 20: Heating device 21: Liquid level sensor 29: Temperature sensor 31:First space part 32:Second space part 41: Raw material solution inlet 42: Carrier gas inlet 43: Exhaust port 44: Outlet 5: Liquid volume control mechanism 51:Liquid mechanism 52:Liquid mechanism 6: Pressure control mechanism 61: Valve gear 70: Raw material container 71: Piping 72:Liquid supply pipe 73: Drain pipe 73a:Tip 74: Exhaust pipe 82: Carrier gas supply pipe 84: Mixed gas supply pipe 89: Concentration sensor G1: Gas G2: Gas G3: Gas L1: Solution L2: Solution L3: Solution

Claims

1. a gas separation membrane that allows the product gas to permeate; a gas separation container having a first space portion that accommodates the separation membrane and stores a raw material solution of the product gas, and a second space portion that is partitioned from the first space portion by the separation membrane; a heating device for heating the separation membrane; a liquid level sensor for detecting a liquid level of the raw material solution in the first space; a liquid volume control mechanism that controls the liquid level of the raw material solution based on the detection result of the liquid level sensor, The gas separation vessel comprises: a carrier gas inlet port communicating with the second space portion and introducing a carrier gas into the second space portion; The gas supply device further includes a delivery port that communicates with the second space and delivers the mixed gas of the carrier gas and the product gas from the second space.

2. 2. The gas supply device according to claim 1, wherein the separation membrane is disposed at a position where it comes into contact with the raw material solution.

3. 2. The gas supply device according to claim 1, wherein the raw material solution is a solution containing raw material components made of polar molecules as raw materials for the product gas.

4. the raw material solution contains hydrazine, hydrogen peroxide, or formic acid as the raw material component, 4. The gas supply device according to claim 3, wherein the mixed gas contains hydrazine, hydrogen peroxide, or formic acid as the product gas.

5. 5. The gas supply device according to claim 1, wherein the separation membrane includes at least one of a zeolite membrane and a metal-organic framework membrane.

6. The gas supply device according to claim 1 , wherein the liquid amount control mechanism includes a supply / discharge mechanism that supplies the raw material solution to the first space portion or discharges the raw material solution from the first space portion.

7. a concentration sensor for measuring the concentration of the product gas contained in the mixed gas; The gas supply device according to claim 1 , further comprising: a pressure control mechanism that controls a pressure of the mixed gas in the second space portion based on a detection result of the concentration sensor.

8. 8. The gas supply device according to claim 7, wherein the pressure control mechanism includes a delivery amount control mechanism that controls the flow rate of the mixed gas delivered from the delivery port.

9. a separation step of contacting a raw solution of the product gas with a gas separation membrane and separating the product gas from the raw solution by permeating the separation membrane; a heating step of heating the separation membrane; a delivery step of introducing a carrier gas into the product gas separated in the separation step and delivering a mixed gas of the product gas and the carrier gas, In the separation step, a liquid level of the raw material solution in contact with the separation membrane is controlled; The gas supply method, wherein the heating step is performed during the separation step.

10. 10. The gas supply method according to claim 9, wherein the raw material solution is a solution containing raw material components made of polar molecules as raw materials for the product gas.

11. the raw material solution contains hydrazine, hydrogen peroxide, or formic acid as the raw material component, The gas supply method according to claim 10 , wherein the mixed gas contains hydrazine, hydrogen peroxide, or formic acid as the product gas.

12. 12. The gas supply method according to claim 9, wherein at least one of a zeolite membrane and a metal-organic structure membrane is used as the separation membrane.

13. 12. The gas supply method according to claim 9, wherein in the delivering step, a pressure of the delivered mixed gas is controlled based on a concentration of the product gas contained in the mixed gas.

Images