PSA device, valuable material manufacturing device, and valuable material manufacturing system

Abstract

[Problem] To provide a PSA device capable of efficiently separating a predetermined gas component from a gas to be treated by reducing thermal energy to be used, a valuable material manufacturing device provided with the PSA device, and a valuable material manufacturing system. [Solution] According to one aspect of the present invention, a PSA device capable of separating a predetermined gas component is provided, the PSA device being provided with an adsorbent that adsorbs the gas component and a container that accommodates the adsorbent. The PSA device is configured to supply a gas to be treated containing the gas component into the container while pressurizing the gas to be treated, and then supply a desorption gas that desorbs the gas component from the adsorbent into the container while depressurizing the inside of the container. The PSA device is set such that, in a graph plotting changes in the pressure inside the container over time, when the area surrounded by the plot while the gas to be treated is being supplied into the container and the horizontal axis passing through a pressure of 0 kPaG is defined as A, and the area surrounded by the plot while the desorption gas is being supplied into the container and the horizontal axis is defined as B, a relationship in which B / A is 5 or less is satisfied.

Description

PSA equipment, valuable materials manufacturing equipment and valuable materials manufacturing system

[0001] This invention relates to a PSA device, a valuable materials manufacturing device, and a valuable materials manufacturing system.

[0002] In recent years, the massive consumption of oils and alcohols produced from petroleum has led to concerns about the depletion of fossil fuel resources and global environmental problems such as the increase in carbon dioxide in the atmosphere. To address these issues, methods for producing organic substances using raw materials other than petroleum, such as the production of bioethanol from edible raw materials like corn through sugar fermentation, are attracting attention. However, such sugar fermentation methods using edible raw materials may lead to soaring food prices because they require limited farmland to be used for non-food production. Therefore, methods are being considered to produce organic substances that were previously made from petroleum using waste materials (garbage) that would otherwise have been discarded.

[0003] For example, Patent Document 1 discloses a method for producing organic substances (valuable materials) by microbial fermentation of synthesis gas containing at least carbon monoxide. Patent Document 1 also discloses that pretreatment of the synthesis gas is performed to remove impurities contained in the synthesis gas prior to microbial fermentation. However, according to the inventors' research, when using a thermal swing adsorption type separation device (TSA) in the pretreatment, there is a problem that a large amount of thermal energy is required. This problem relates to the purification of synthesis gas and also applies similarly when producing organic substances (valuable materials) from synthesis gas using a catalyst.

[0004] Re-table 2019 / 188730 publication

[0005] In view of the above circumstances, the present invention aims to provide a PSA apparatus capable of efficiently separating predetermined gas components from a gas to be treated while reducing the amount of thermal energy used, a valuable materials manufacturing apparatus equipped with such a PSA apparatus, and a valuable materials manufacturing system.

[0006] According to one aspect of the present invention, a PSA apparatus capable of separating predetermined gas components is provided, comprising an adsorbent for adsorbing gas components and a container for containing the adsorbent, configured to supply a gas to be treated containing gas components into the container under pressurized conditions, and then supply a release gas that separates the gas components from the adsorbent into the container while depressurizing the inside of the container, wherein in a graph plotting the pressure change inside the container over time, the area enclosed by the graph while the gas to be treated is supplied into the container and the horizontal axis passing through a pressure of 0 kPaG is defined as A, and the area enclosed by the graph while the release gas is supplied into the container and the horizontal axis is defined as B, and the apparatus is configured to satisfy the relationship B / A being 5 or less.

[0007] According to this embodiment, predetermined gas components can be efficiently separated from the gas to be treated while reducing the amount of thermal energy used.

[0008] This is a schematic diagram showing the configuration of the valuable materials manufacturing system according to the first embodiment. This is a schematic diagram showing the configuration of the PSA device in the valuable materials manufacturing system according to the first embodiment. This is a graph showing the pressure change inside the container of the PSA device according to the first embodiment. This is a schematic diagram showing the configuration of the PSA device in the valuable materials manufacturing system according to the second embodiment. This is a schematic diagram showing the configuration of the PSA device in the valuable materials manufacturing system according to the third embodiment. This is a schematic diagram showing the configuration of the PSA device in the valuable materials manufacturing system according to the fourth embodiment. This is a schematic diagram showing the configuration of the PSA device in the valuable materials manufacturing system according to the fifth embodiment. This is a schematic diagram showing the configuration of the PSA device in the valuable materials manufacturing system according to the sixth embodiment. This is a schematic diagram showing the configuration of the container of the PSA device according to the sixth embodiment. This is a diagram relating to the configuration of the PSA device used in the simulation. This is a graph showing the simulation results for Case 1. This is a graph showing the simulation results for Case 2. This is a graph showing the relationship between the change in total purge gas flow rate and the concentration of carbon dioxide contained in the recovered gas ((a) Case 1, (b) Case 2). This is a graph showing the simulation results for Case 3.

[0009] The PSA apparatus, the valuable material manufacturing apparatus, and the valuable material manufacturing system will be described in detail below based on the preferred embodiments shown in the attached drawings. <First Embodiment> First, the valuable material manufacturing system according to the first embodiment will be described. Figure 1 is a schematic diagram showing the configuration of the valuable material manufacturing system according to the first embodiment. Figure 2 is a schematic diagram showing the configuration of the PSA apparatus in the valuable material manufacturing system according to the first embodiment. Figure 3 is a graph showing the pressure change inside the container of the PSA apparatus according to the first embodiment.

[0010] The valuable material manufacturing system 100 shown in Figure 1 (hereinafter also simply referred to as "manufacturing system 100") comprises a gasifier (gas generation unit that generates raw material gas) 10 and a valuable material manufacturing device 1 (hereinafter also simply referred to as "manufacturing device 1") connected to the gasifier 10. In this specification, the upstream side with respect to the flow direction of gas and liquid is simply referred to as the "upstream side," and the downstream side is simply referred to as the "downstream side." In this embodiment, the gasifier 10 is not particularly limited, but examples include fluidized bed furnaces, kiln furnaces, shaft furnaces, etc. In addition to the gasifier 10, the gas generation unit also includes CO2 from at least one business establishment selected from combustion furnaces (incinerators), paper mills, cement mills, thermal power plants, oil refineries, ethylene crackers, oil refineries, chemical plants, and blast furnaces, converters, or electric furnaces in steel mills. Ｘ It may also be a source of emissions. In each furnace, raw material gas containing carbon monoxide and carbon dioxide (hereinafter also simply referred to as "raw material gas") is generated during the combustion, melting, and refining of the contents.

[0011] In the case of a combustion furnace or gasification furnace 10 in a waste incineration plant, examples of contents (waste) include plastic waste, food waste, municipal waste (MSW), industrial waste, discarded tires, biomass waste, household waste (futons, paper products), building materials, etc. These wastes may consist of one type alone or two or more types. In the case of a blast furnace, converter, or electric furnace in a steel mill, for example, raw material gas is generated when iron ore is heated together with coke, limestone, etc. In the case of a chemical plant, for example, raw material gas is generated when methane is steam reformed or when binders are removed during the manufacture of ceramic sintered bodies.

[0012] The carbon in raw material gas derived from waste, etc., is different from the carbon in petroleum. １４ C, １３ The abundance of carbon isotopes such as C (e.g., δ １４ C, δ １３ The C values ​​are different. Therefore, the ratio of carbon isotopes contained in the valuable product produced by the production system 100 from such raw gas is also different from that of the valuable product derived from petroleum. Consequently, even if the valuable product produced by the production system 100 is converted into other compounds and used, it can be identified (traceable) that it originated from the valuable product produced by the environmentally friendly method of the production system 100.

[0013] The raw material gas may typically contain other gaseous components such as nitrogen, hydrogen, oxygen, water vapor, and methane, in addition to carbon monoxide and carbon dioxide. The raw material gas may further contain other components such as soot, tar, nitrogen compounds, sulfur compounds, phosphorus compounds, halogen compounds, cyanide compounds, monocyclic aromatic compounds, and polycyclic aromatic compounds. The raw material gas may be produced as a gas containing 10% or more by volume by performing a heat treatment (commonly known as gasification) that causes incomplete combustion of the contents (carbon source) (i.e., partially oxidizing the carbon source). By manufacturing valuable products using such a raw material gas, carbon dioxide that was conventionally emitted into the atmosphere can be effectively utilized, and the burden on the environment can be reduced. From the viewpoint of carbon cycling, it is preferable to use exhaust gas generated in a combustion furnace or smelter as the raw material gas.

[0014] The gasifier 10 may have an oxygen generator that produces the oxygen necessary for combustion. Examples of oxygen generators include cryogenic separation devices that can compress, cool, and liquefy air from the atmosphere to extract liquid oxygen, liquid nitrogen, etc. The heat absorbed when the obtained liquid nitrogen vaporizes can be used to cool parts of the manufacturing system 100. In addition, the nitrogen gas obtained when liquid nitrogen vaporizes can be suitably used as a purge gas for various parts of the manufacturing system 100.

[0015] Furthermore, the gasification furnace 10 may have a reforming area inside or outside it for reforming the raw material gas. In the reforming area, for example, by keeping the raw material gas at a high temperature, hydrocarbons (methane, ethane, char, tar, dioxins, etc.) contained in the raw material gas are converted into carbon monoxide and hydrogen. At this time, a combustion-supporting gas such as oxygen or air may be supplied to raise the temperature. Furthermore, some of the carbon monoxide may be converted into carbon dioxide by reacting with oxygen. The temperature is preferably 1000°C or higher, and more preferably 1100°C to 1400°C.

[0016] In the reforming area, a method may be employed in which hydrocarbons such as methane contained in the raw material gas are reacted with water vapor at a high temperature in the presence of a catalyst to convert them into carbon monoxide and hydrogen. At this time, some of the carbon monoxide may be further converted into carbon dioxide and hydrogen by reacting with water vapor. The reaction temperature is preferably 500°C to 1200°C. Examples of catalysts include metal catalysts. Examples of metal catalysts include nickel catalysts, nickel oxide catalysts, ruthenium catalysts, rhodium catalysts, palladium catalysts, and platinum catalysts.

[0017] Here, the stable isotope ratio of carbon δ １３ It is known that carbon (C) tends to have a higher value under high-temperature combustion conditions and a lower value under incomplete combustion conditions. Therefore, by providing a reforming area, the raw material gas can be reformed to produce a unique δ (δ) according to the combustion conditions. １３ It may have a C value. Therefore, even if the valuable material produced by the manufacturing system 100 is converted into other compounds and used, it can be identified (trace) that it originated from the valuable material produced by the manufacturing system 100 using an environmentally friendly method.

[0018] The raw material gas (synthesis gas) generated by the gasifier 10 is at a high temperature. The heat of this high-temperature raw material gas may be utilized to generate steam from water. For example, a tank storing water may be provided in the middle of the gas line GL1 connected to the downstream side of the gasifier 10, and steam may be generated by heat exchange between the raw material gas and water. Also, a heat recovery device (for example, an economizer, a heat pump, etc.) more suitable for recovering the high-temperature heat provided near the gas line GL1 near the outlet of the gasifier 10 may be used to generate steam by heat exchange with the raw material gas. Thus, by efficiently recovering and utilizing the heat of the raw material gas without leaving any, the environmental load during the production of valuable substances can be further reduced. Note that the heat of the raw material gas is not limited to the utilization for the above purpose and can be utilized for various purposes. Also, the heat of the gas discharged from the reforming area may be recovered. As a heat recovery method, when a scrubber is used for cooling, the heat energy recovered through the scrubber may be utilized.

[0019] Such a gasifier 10 is connected to the production device 1. This production device 1 includes a culture tank (valuable substance generation section) 2, a purification device 6, a gas line GL1 connecting the gasifier 10 and the culture tank 2, and a liquid line LL connecting the culture tank 2 and the purification device 6. In the culture tank 2, valuable substances are generated using microorganisms (particularly, gas-utilizing bacteria or algae) from carbon monoxide contained in the supplied raw material gas. That is, in the culture tank 2, valuable substances are generated by microbial fermentation of the raw material gas.

[0020] Here, since the valuable substances generated in the culture tank 2 are generated using carbon derived from the raw material gas, they are different from valuable substances derived from petroleum １４ C, １３ the abundance ratio of carbon isotopes such as C (for example, δ １４ C, δ １３ the value of C) is different. Therefore, even if this valuable substance is converted and used in products such as other compounds, it can be discriminated (traced) that it is derived from valuable substances generated by a method with a low environmental load by the production system 100.

[0021] Examples of gas-assimilating bacteria include, for example, Butyribacterium methylotrophicum, Clostridium autoethanogenum, Clostridium carboxidivorans, Clostridium ljungdahlii, Clostridium ragsdalei, Moorella, Carboxydothermus, etc. Examples of algae include, for example, cyanobacteria, Chlorella, Botryococcus, Nannochloropsis, Haematococcus, Scenedesmus, Stichococcus, Nannochloris, Desmodesmus, etc.

[0022] When using microorganisms such as gas-assimilating bacteria and algae, the １４ C, １３ The abundance ratio of carbon isotopes such as C (for example, δ １４ C, δ １３ C value) can be made to deviate more significantly from the value of petroleum-derived products. Therefore, even if the produced valuable substance is converted into other compounds and used, it is easier to discriminate (trace) that it is derived from the valuable substance produced by the method with a low environmental impact by the production system 100.

[0023] The medium (culture solution) used for culturing microorganisms is not particularly limited as long as it has an appropriate composition according to the type. When using Clostridium bacteria as gas-assimilating bacteria, for the medium, for example, paragraphs 0097 to 0098 of US Patent Application Publication No. 2017 / 260552 can be referred to. For the culture tank 2, for example, a culture reactor of the type that stirs the culture solution with a stirring plate, a culture reactor of the type that stirs the culture solution by circulating the culture solution itself, a culture reactor of the type that stirs the culture solution by the water flow accompanying the bubble flow generated by the aeration of the supplied raw material gas, etc. can be used.

[0024] Furthermore, the valuable substance generation section may be composed of a reactor containing a catalyst instead of the culture tank 2. In this case, examples of catalysts include ruthenium, rhodium, manganese, germanium, tantalum, zirconium, niobium, hafnium, lanthanum, cerium, aluminum, magnesium, copper, zinc, silicon, or oxides thereof. These substances may be used individually or in combination of two or more.

[0025] The manufacturing apparatus 1 includes a pre-processing section located in the middle of the gas line GL1 (i.e., between the gasification furnace 10 and the culture tank 2). This pre-processing section comprises a filter device 3, a PSA device 4, and a catalyst device 5, arranged in order from the gasification furnace 10 side (upstream side). The filter device 3 is used to remove tar, soot, and fine particles smaller than the size of soot. This filter can be made of, for example, a bag filter.

[0026] The catalyst device 5 is primarily used to remove oxygen and acetylene. For the oxygen removal catalyst, metal particles such as copper (Cu), platinum (Pt), and nickel (Ni) can be used. It is preferable to heat the oxygen removal catalyst to a temperature of 150°C to 400°C. For the acetylene removal catalyst, precious metal particles such as palladium (Pd) and platinum (Pt) can be used. It should be noted that removing acetylene prior to deoxygenation has the advantage of effectively preventing or reducing the adverse effects of acetylene on the oxygen removal catalyst.

[0027] The PSA device 4 is a pressure swing adsorption separator capable of separating a predetermined gas component. The PSA device 4 of the present embodiment can separate at least carbon dioxide from a raw material gas (a processed gas containing a gas component) containing carbon monoxide and carbon dioxide. That is, in the present embodiment, the gas component contains at least carbon dioxide. Then, the raw material gas from which at least carbon dioxide has been separated is supplied to the culture tank (valuable substance generation unit) 2 after passing through the catalyst device 5. As shown in FIG. 2, the PSA device 4 includes a container 40 provided in the middle of the gas line GL1. The gas line GL1 is composed of a gas line GL11 and a gas line GL12. The gas line GL11 connects the filter device 3 and the lower port 401 of the container 40. In the middle of this gas line GL11, an air supply pump (compressor) P1 and a valve V1 are provided in order from the upstream side.

[0028] The gas line GL12 connects the upper port 402 of the container 40 and the catalyst device 5. A valve V2 is provided in the middle of this gas line GL12. According to such a configuration, while pressurizing the raw material gas by the action of the air supply pump P1, it can be supplied into the container 40 through the gas line GL1 and further passed through the container 40. In addition, a gas line GL2 is connected to the lower port 401 of the container 40. In the middle of this gas line GL2, a valve V5 and a decompression pump P2 are provided in order from the container 40 side. That is, the decompression pump P2 is connected to the lower port 401 of the container 40 (the side where the raw material gas is supplied). According to such a configuration, the inside of the container 40 can be decompressed through the gas line GL2 by the action of the decompression pump P2. A gas-liquid separation section, a cooling section, etc. may be arranged between the decompression pump and the PSA device. It can be expected that the above-mentioned gas-liquid separation section or cooling section suppresses the reaction of hydrogen sulfide and water to generate corrosive liquids such as sulfuric acid. It can also be expected that the corrosive liquid formed by the reaction of hydrogen sulfide or the like coming out of the PSA by cooling or the like can reduce the reaction rate of the corrosive action by the corrosive liquid as the temperature is lower.

[0029] The container 40 contains (places) an adsorbent 4a that adsorbs at least carbon dioxide (gas component) from the raw gas. In this embodiment, the container 40 and the adsorbent 4a contained within the container 40 constitute one adsorption tower. The adsorbent 4a can be separated by depressurizing the container 40 with a vacuum pump P2, which mainly releases carbon dioxide from the adsorbent 4a. The adsorbent 4a can be composed of one or more of the following: zeolite, bentonite, sericite, perlite, coral reef rock, vermiculite, silica gel, molecular sieves, activated carbon, MOF (metal-organic frame), etc. Among these, it is preferable that the adsorbent 4a be composed of zeolite. This is because zeolite has particularly excellent carbon dioxide adsorption and release capabilities. Furthermore, when using zeolite, zeolites with multiple structures may be used. As mentioned above, one method of using multiple types of zeolites is to place a zeolite that readily adsorbs water in the front stage and a zeolite that readily adsorbs hydrogen sulfide and carbon dioxide but not water in the back stage. As mentioned above, by arranging zeolites with different properties, water, hydrogen sulfide, and carbon dioxide can be efficiently removed from the synthesis gas containing carbon monoxide and hydrogen. Furthermore, the adsorbent may partially adsorb carbon monoxide or hydrogen. Placing an adsorbent that readily adsorbs water molecules in the front stage is preferable because it suppresses the generation of corrosive products that occur when water molecules react with sulfide compounds. In addition, if the adsorbent also adsorbs at least some of the carbon monoxide, the carbon monoxide released when the adsorbent is regenerated by flowing nitrogen as a purge gas may be further separated and combined with the synthesis gas flowing in the back stage. As mentioned above, by separating the released carbon monoxide from hydrogen sulfide and other substances and then combining it with the synthesis gas, the proportion of carbon monoxide in the synthesis gas can be controlled, and the amount of ethanol produced from a unit amount of waste can be increased.

[0030] The average particle size of the adsorbent 4a is preferably 0.5 mm or more and 10 mm or less, more preferably 0.8 mm or more and 8 mm or less, and even more preferably 1 mm or more and 6 mm or less. In this case, the contact area of ​​the adsorbent 4a with the raw material gas can be sufficiently large. The shape is not limited to spherical, but may be cylindrical, for example. In this specification, the average particle size means the average value of the particle sizes of any 200 particles in a single field of view observed with an electron microscope. In this case, "particle size" means the maximum distance between two points on the contour line of the particle.

[0031] Furthermore, the BET specific surface area of ​​the adsorbent 4a is 50 m². ２ / g or more 1200m ２ It is preferable that it be less than or equal to 100m ２ / g or more 1000m ２ It is more preferable that it be less than or equal to 200m ２ / g or more 800m ２ It is even more preferable that the amount is less than or equal to / g. In this case, the contact area of ​​the adsorbent 4a with the raw material gas can be sufficiently large. In this specification, the BET specific surface area is a value measured using a BET specific surface area meter in accordance with the BET single-point method ("Method for measuring the specific surface area of ​​fine ceramic powder by gas adsorption BET method" as specified in JIS R 1626:1996).

[0032] The average pore size of the adsorbent 4a is preferably 1 Å or more and 20 Å or less, more preferably 3 Å or more and 18 Å or less, and even more preferably 5 Å or more and 15 Å or less. In this case, the contact area of ​​the adsorbent 4a with the raw material gas can be sufficiently large. In this specification, the average pore size is a value measured by pore size distribution measurement using the mercury intrusion method with a mercury porosimeter.

[0033] If the raw material gas further contains water vapor, sulfur compounds, polycyclic aromatic compounds, and tar, the PSA device 4 (adsorbent 4a) may be configured to adsorb and separate water vapor, sulfur compounds, polycyclic aromatic compounds, and tar as well. This prevents adverse effects on the growth of microorganisms. Examples of sulfur compounds include hydrogen sulfide, carbonyl sulfide, mercury sulfide, sulfur dioxide, sulfur trioxide, sulfur hexafluoride, sulfur dichloride, and sodium thiosulfate. Examples of polycyclic aromatic compounds include naphthalene, anthracene, phenanthrene, tetracene, pentacene, chrysene, and benzopyrene.

[0034] A purge gas supply unit 43 is connected to the container 40 on the opposite side from where the raw material gas is supplied. This unit supplies a purge gas (a release gas that releases gas components from the adsorbent 4a). In this embodiment, the purge gas supply unit 43 is connected to the upper port 402 of the container 40 via a gas line GL4. A valve V7 is also provided in the middle of the gas line GL4. With this configuration, the purge gas can be supplied into the container 40 while the pressure inside the container 40 is reduced by the action of the depressurizing pump P2. This allows the adsorbent 4a to be cleaned and regenerated. Here, it is preferable that the purge gas (release gas) includes at least one selected from the group consisting of gases that do not easily adsorb or react with the adsorbent 4a, i.e., nitrogen and inert gases (rare gases such as argon and helium). The flow path of the purge gas may have a gas component analysis unit and a gas switching unit. The purge gas switching unit may include a configuration in which the gas flow path is switched to reuse the purge gas if the amount of impurities is below a predetermined value after measuring the composition of the gas that comes out after the purge gas has been introduced into the PSA device.

[0035] Furthermore, a thermometer TE is connected to the container 40, allowing the temperature inside the container 40 to be measured. Pressure gauges PT are connected to the lower port 401 and upper port 402 of the container 40, respectively, allowing the pressure of the gas supplied to and discharged from the container 40 to be measured.

[0036] The carbon dioxide reduction rate, calculated from the carbon dioxide concentration in the raw material gas processed in the pre-processing unit and the carbon dioxide concentration in the raw material gas introduced into the pre-processing unit, is preferably 40% or more, more preferably 60% or more, and even more preferably 85% or more, when 100% is defined as the rate at which a purge gas adjusted to a flow rate of 10% of the raw material gas flow rate is flowed for 25 minutes. The time for supplying the purge gas into the container 40 (purge time) is not particularly limited, as long as the carbon dioxide reduction rate can be adjusted to satisfy the above range. Therefore, the carbon dioxide removal rate can be adjusted by appropriately setting the purge gas flow rate and purge time to satisfy the above range.

[0037] The raw material gas processed in the pre-treatment unit is supplied to the culture tank 2 or the reactor. For example, when the raw material gas is supplied to the culture tank 2, an improvement in the resource efficiency of carbon monoxide can be expected. In addition, the carbon monoxide concentration in the raw material gas is sufficiently high because carbon dioxide is mainly separated (removed) in the PSA device 4. Therefore, valuable materials can be produced more efficiently in the culture tank 2. Furthermore, since the overall volume of the raw material gas is reduced, the size of piping, pumps, containers, etc., located in the pre-treatment unit and / or downstream thereof can also be reduced.

[0038] The culture tank (valuable substance generation unit) 2 is configured to generate valuable substances, specifically a valuable substance-containing liquid, from raw material gas using microorganisms (gas-assimilating bacteria or algae). A purification device 6 is connected to the culture tank 2 via a liquid line LL. This purification device 6 is a device that purifies valuable substances (organic substances) from the valuable substance-containing liquid. Examples of such a purification device 6 include a distillation device, a processing device including a permeable vaporization membrane, a zeolite dehydration membrane, a processing device including an organic membrane, a processing device that removes low-boiling point substances with a boiling point lower than the valuable substances, a processing device that removes high-boiling point substances with a boiling point higher than the valuable substances, and a processing device including an ion exchange membrane. These devices may be used individually or in combination of two or more types.

[0039] When using a distillation apparatus, for example, the temperature inside the distillation apparatus during the distillation of ethanol, a valuable substance, is not particularly limited, but it is preferably above the boiling point corresponding to the pressure and 100°C or less, and more preferably between 40°C and 95°C. By setting the temperature in this manner, the separation of the necessary valuable substance from other components, i.e., the distillation (purification) of the valuable substance, can be carried out more reliably. Here, the boiling point corresponding to the pressure is, for example, about 66°C at 60 kPaA. The pressure inside the distillation apparatus during the distillation of the valuable substance may be atmospheric pressure, but it is preferably below atmospheric pressure (reduced pressure distillation), and more preferably between 60 kPaA and 95 kPaA. By setting the pressure in this manner, the separation efficiency of the valuable substance can be improved, and consequently, the yield of the valuable substance can be improved. Furthermore, for purification, membrane separation or membrane concentration may be performed using membranes such as zeolite membranes, carbon membranes, ceramic membranes, silica membranes, or polymer membranes (e.g., polyimide membranes).

[0040] Furthermore, for example, the temperature inside the distillation apparatus during the distillation of acetic acid, a valuable substance, is not particularly limited, but is preferably 95°C or higher, and more preferably 100°C to 150°C. The pressure inside the distillation apparatus during the distillation of the valuable substance may be atmospheric pressure, but is preferably less than atmospheric pressure (reduced pressure distillation), and more preferably 60 kPaA to 95 kPaA. By setting the pressure in this manner, the separation efficiency of the valuable substance can be improved, and consequently, the yield of the valuable substance can be improved. In addition, azeotropes and the like may be added to the liquid containing the valuable substance. The yield of the valuable substance (concentration of the valuable substance in the purified product) is preferably 90% by mass or higher, more preferably 99% by mass or higher, and even more preferably 99.5% by mass or higher. For purification, as with ethanol, membrane separation or membrane concentration may be performed using membranes such as zeolite membranes, carbon membranes, ceramic membranes, silica membranes, and polymer membranes (e.g., polyimide membranes).

[0041] The valuable substances obtained in this way include, for example, monools such as methanol and ethanol, diols such as 2,3-butanediol, acetic acid, lactic acid, isoprene, and butadiene, and are preferably monools or diols having 1 to 4 carbon atoms, and more preferably ethanol. Such valuable substances can be used, for example, as raw materials for resin materials, rubber materials, etc., and can also be used as various solvents, disinfectants, or fuels. High-concentration ethanol can be used as fuel ethanol mixed with gasoline, etc., and can also be used as a raw material for cosmetics, beverages, chemicals, fuels (jet fuel), etc., and as an additive for food, etc., making it extremely versatile.

[0042] Next, the operation method of the PSA device 4 will be explained. As described above, the PSA device 4 is configured to supply the raw material gas (the gas to be treated, including gaseous components) into the container 40 under pressurization by the action of the air supply pump P1, and then to supply a purge gas (detachment gas) into the container 40, mainly to detach carbon dioxide (gasic component) from the adsorbent 4a, while depressurizing the container 40 by the action of the depressurization pump P2. As shown in Figure 3, in a graph G plotting the change in pressure inside the container 40 over time, with the x-axis as time [hours] and the y-axis as pressure inside the container 40 [kPaG], the area enclosed by graph G and the x-axis while the raw material gas is being supplied into the container 40 is A [kPaG・hours], and the area enclosed by graph G and the x-axis while the purge gas is being supplied into the container 40 is B [kPaG・hours], and the PSA device 4 is configured to satisfy the relationship that B / A is 5 or less.

[0043] By setting it in this way, the amount of purge gas used can be sufficiently reduced without reducing the concentration of carbon monoxide (carbon monoxide recovery rate) in the recovered gas, which is the raw material gas after passing through the PSA device 4. The B / A ratio only needs to satisfy the relationship of 5 or less, but it is preferable that it satisfies the relationship of 2.5 or less. The B / A ratio is preferably 0.1 or more, and more preferably 0.25 or more. For example, the B / A ratio can be 0.1 or more and 5 or less. This can further improve the above effect, and in particular, the adsorbent 4a can be regenerated efficiently.

[0044] The maximum pressure inside the container 40 when supplying the raw material gas is preferably 10 kPaG or more and 200 kPaG or less, more preferably 20 kPaG or more and 150 kPaG or less, and even more preferably 30 kPaG or more and 100 kPaG or less. By setting the maximum pressure inside the container 40 within the above range, the amount of adsorption of carbon dioxide and the like onto the adsorbent 4a can be sufficiently increased regardless of the flow rate (supply speed) of the raw material gas into the container 40. Furthermore, the time for supplying the raw material gas into the container 40 (feed time) is preferably 1 minute or more and 60 minutes or less, more preferably 5 minutes or more and 50 minutes or less, and even more preferably 10 minutes or more and 40 minutes or less. Here, in this specification, the time for supplying the raw material gas into the container 40 is defined as the time from time t1 to time t2, as shown in Figure 3, during which the pressure inside the container 40 rises from 0 kPaG and then falls back down to 0 kPaG.

[0045] When supplying the raw material gas into the container 40, the flow rate per volume of adsorbent (space velocity of the raw material gas) is preferably 10 / hour or more and 1000 / hour or less, more preferably 50 / hour or more and 800 / hour or less, and even more preferably 100 / hour or more and 500 / hour or less. In this case, a sufficient amount of valuable raw material (assimilable raw material) can be obtained. The temperature of the raw material gas supplied into the container 40 is not particularly limited, but is preferably 0°C or more and 60°C or less, more preferably 5°C or more and 50°C or less, and even more preferably 10°C or more and 40°C or less. By setting the temperature of the raw material gas within the above temperature range, carbon dioxide and the like can be efficiently adsorbed onto the adsorbent 4a while preventing thermal degradation of the adsorbent 4a.

[0046] When supplying purge gas (release gas) into the container 40, the pressure inside the container 40 during depressurization (minimum pressure) is preferably -100 kPaG or higher, more preferably -95 kPaG or higher and -30 kPaG or lower, and even more preferably -90 kPaG or higher and -40 kPaG or lower. By setting the minimum pressure inside the container 40 within the above range, the energy required to operate the depressurization pump P2 can be reduced, or a relatively inexpensive pump can be used. Furthermore, the time for supplying purge gas into the container 40 (purge time) is preferably 0.1 to 1.5 times the time for supplying raw material gas into the container 40 (feed time), more preferably 0.2 to 1.25 times, and even more preferably 0.3 to 1 time. Specifically, the time is preferably 1 minute to 60 minutes, more preferably 3 minutes to 40 minutes, and even more preferably 5 minutes to 30 minutes. By maintaining the flow rate of purge gas supplied into the container 40, even if the time for supplying purge gas into the container 40 is shortened, carbon dioxide and the like can be smoothly released from the adsorbent 4a, that is, a high regeneration effect of the adsorbent 4a can be obtained. Here, in this specification, the time for supplying purge gas into the container 40 is defined as the time from time t3 to time t4, as shown in Figure 3, when the pressure inside the container 40 reaches the minimum pressure due to the action of the depressurizing pump P2 and maintains that minimum pressure.

[0047] The flow rate of the purge gas when supplying it into the container 40 (purge gas flow rate) is preferably 0.1% to 25% of the flow rate of the raw material gas when supplying it into the container 40 (raw material gas flow rate), more preferably 0.2% to 20%, and even more preferably 0.3% to 15%. For example, the purge gas flow rate is when the raw material gas flow rate is 300 Nm³. ３ In the case of time, 25 Nm ３ Preferably less than / hour, and 10 Nm ３ / hour or more 20Nm ３ It is more preferable that the time be less than or equal to 15 Nm ３ / hour or more 20Nm ３It is even more preferable that the time for supplying the purge gas into the container 40 is less than or equal to the time per hour. If the time for supplying the purge gas into the container 40 is sufficiently maintained, a high regeneration effect of the adsorbent 4a can be obtained even if the flow rate of the purge gas supplied into the container 40 is reduced. The temperature of the purge gas supplied into the container 40 is not particularly limited, but it is preferably 5°C to 150°C, more preferably 10°C to 140°C, and even more preferably 20°C to 130°C. By setting the temperature of the purge gas within the above temperature range, it is possible to prevent thermal degradation of the adsorbent 4a while obtaining a high regeneration effect of the adsorbent 4a.

[0048] The PSA apparatus 4 may further include a cooling mechanism (not shown) for cooling the adsorbent 4a. By providing such a cooling mechanism, the gas density of the raw material gas processed in the PSA apparatus 4 can be increased. As a result, the amount of carbon monoxide supplied to the culture tank 2 can also be increased, and thus an increase in the amount of valuable substances produced can be expected. Furthermore, by cooling the adsorbent, corrosion reactions due to the reaction of water and sulfide compounds in the adsorbent containment can be suppressed. This cooling mechanism can be composed of, for example, a pipe for circulating a refrigerant arranged along the outer circumference of the container 40 or through the container 40, and a pump for circulating this refrigerant.

[0049] Next, the method of using the manufacturing system 100 of the first embodiment (method of manufacturing valuable materials) will be described. [1] First, the raw material gas (raw material gas containing carbon monoxide, carbon dioxide and other gaseous components) discharged from the gasification furnace 10 is supplied to the filter device 3. At this time, minute solid matter (for example, tar, soot, etc.) contained in the raw material gas is removed. [2] Next, valves V1 and V2 are opened, and valves V5 and V7 are closed, and the air supply pump P1 is operated. As a result, the raw material gas discharged from the filter device 3 is supplied to the container 40 while being pressurized, and passes through it. At this time, carbon dioxide is mainly adsorbed by the adsorbent 4a.

[0050] [3] The raw material gas from which carbon dioxide and other substances have been separated (hereinafter also referred to as "recovered gas") then passes through the catalyst device 5. At this time, oxygen and acetylene are removed from the raw material gas. [4] The raw material gas that has passed through the pretreatment device is then supplied to the culture tank 2. In the culture tank 2, valuable substances are produced from carbon monoxide contained in the supplied raw material gas by the action of microorganisms. This yields a liquid containing valuable substances. Here, the temperature at which valuable substances are produced from carbon monoxide in the culture tank 2 (microorganism culture temperature) is not particularly limited, but it is preferably 25°C or higher and 50°C or lower.

[0051] [5] Next, the liquid containing valuable substances obtained in the culture tank 2 is supplied to the purification device 6 via the liquid line LL. In the purification device 6, the valuable substances contained in the liquid containing valuable substances are purified, and a purified product containing valuable substances at a high concentration is obtained. [6] When the performance of the adsorbent 4a deteriorates after a predetermined time has elapsed, valves V1 and V2 are closed, valve V5 is opened, and the vacuum pump P2 is activated. This releases and separates carbon dioxide and other substances from the adsorbent 4a etc. in the container 40. As a result, off-gas containing carbon dioxide and other substances can be recovered.

[0052] At this time, valve V7 is opened to supply purge gas from the purge gas supply unit 43 to the container 40. This increases the efficiency of removing carbon dioxide and other substances from the adsorbent 4a, allowing the adsorbent 4a to be cleaned. Furthermore, by optimizing the material, average particle size, BET specific surface area, average pore diameter, density, temperature resistance, and shape of the adsorbent 4a, the degree of depressurization by the depressurization pump P2 can be reduced.

[0053] <Second Embodiment> Next, a manufacturing system for valuable materials according to the second embodiment will be described. The manufacturing system for valuable materials according to the second embodiment will be described below, focusing on the differences from the manufacturing system for valuable materials of the first embodiment, and similar matters will be omitted from the description. Figure 4 is a schematic diagram showing the configuration of the PSA device in the manufacturing system for valuable materials according to the second embodiment. In the manufacturing system 100 of the second embodiment, the configuration of the PSA device is different, but otherwise it is the same as the manufacturing system 100 of the first embodiment.

[0054] In the second embodiment, as shown in Figure 4, there is a first PSA device 41 and a second PSA device 42. The first PSA device 41 and the second PSA device 42 are each provided with a first container 410a and a second container 420a, respectively, located in the middle of the gas line GL1, starting from the upstream side. The gas line GL1 is composed of gas line GL11, gas line GL12, and gas line GL13. Gas line GL11 connects the filter device 3 to the lower port 411a of the first container 410a. In the middle of this gas line GL11, a supply pump (compressor) P1 and a valve V1 are provided, starting from the upstream side.

[0055] Gas line GL12 connects the upper port 412a of the first container 410a to the lower port 421a of the second container 420a. Valves V2 and V3 are provided along gas line GL12, in order from the upstream side. Gas line GL13 connects the upper port 422a of the second container 420a to the catalyst device 5. Valve V4 is provided along gas line GL13. With this configuration, the raw material gas can be sequentially passed through the first container 410a and the second container 420a via gas line GL1.

[0056] Furthermore, a gas line GL2 is connected to the lower port 411a of the first container 410a. Along this gas line GL2, a valve V5 and a pressure reducing pump P2 are provided in order from the first container 410a side. That is, the pressure reducing pump P2 is connected to the lower port 411a of the first container 410a (the side to which the raw material gas is supplied). A gas line GL3 is connected to the lower port 421a of the second container 420a. Along this gas line GL3, a valve V6 and a pressure reducing pump P3 are provided in order from the second container 420a side. That is, the pressure reducing pump P3 is connected to the lower port 421a of the second container 420a (the side to which the raw material gas is supplied).

[0057] With this configuration, the pressure inside the first container 410a can be reduced via the gas line GL2 by the action of the pressure reducing pump P2, and the pressure inside the second container 420a can be reduced via the gas line GL3 by the action of the pressure reducing pump P3. In other words, in this embodiment, a pressure reducing mechanism is configured that can reduce the pressure inside the first container 410a and the second container 420a using the pressure reducing pumps P2 and P3. In this embodiment, the second container 420a contains (is arranged) a second adsorbent 42a similar to the adsorbent 4a described above.

[0058] On the other hand, the first container 410a contains (arranges) a first adsorbent 41a capable of adsorbing at least monocyclic aromatic compounds in the raw material gas. The first adsorbent 41a can be separated by depressurizing the first container 410a with a vacuum pump P2, thereby releasing the monocyclic aromatic compounds from the first adsorbent 41a. Examples of monocyclic aromatic compounds include benzene, toluene, ethylbenzene, xylene, aniline, nitrobenzene, cumene, benzenesulfonic acid, chlorobenzene, benzoic acid, trinitrotoluene, styrene, etc., and the first adsorbent 41a may contain one or more of these. The first adsorbent 41a can be composed of the same substances as those listed for adsorbent 4a. Preferably, the first adsorbent 41a is composed of activated carbon. This is because activated carbon has particularly excellent adsorption and desorption capabilities for monocyclic aromatic compounds.

[0059] The average particle size of the first adsorbent 41a is preferably 0.5 mm or more and 10 mm or less, more preferably 0.8 mm or more and 8 mm or less, and even more preferably 1 mm or more and 6 mm or less. The BET specific surface area of ​​the first adsorbent 41a is 100 m². ２ / g or more 2500m ２ It is preferable that the amount be less than or equal to 200m ２ / g or more 2000m ２ It is more preferable that it be less than or equal to 300m ２ / g or more 1500m ２It is even more preferable that the amount is less than or equal to / g. The average pore size of the first adsorbent 41a is preferably 1 Å to 300 Å, more preferably 3 Å to 250 Å, and even more preferably 5 Å to 200 Å. By appropriately setting these numerical ranges, the contact area of ​​the first adsorbent 41a with the raw material gas can be sufficiently increased.

[0060] If the raw material gas further contains halogen compounds and cyanide compounds, it is preferable that the first PSA device 41 is configured to adsorb and separate halogen compounds and cyanide compounds as well. This prevents adverse effects on the growth of microorganisms. Examples of halogen compounds include hydrogen chloride, hydrogen fluoride, chlorine, fluorine, and bromine. Examples of cyanide compounds include hydrogen cyanide and nitriles. The first adsorbent 41a can be configured to adsorb not only monocyclic aromatic compounds but also halogen compounds and cyanide compounds by appropriately setting its material, average particle size, BET specific surface area, average pore diameter, density, temperature resistance, shape, etc.

[0061] In this embodiment, the first container 410a further contains (is arranged) a protective agent 41b that is capable of adsorbing water vapor, sulfur compounds, polycyclic aromatic compounds, and tar, and protects the first adsorbent 41a. By housing the protective agent 41b in the first container 410a, in addition to the above effects, the effect of preventing or suppressing the deterioration of the performance of the first adsorbent 41a over time can also be obtained. Note that the protective agent 41b may be housed in a container other than the first container 410a that houses the first adsorbent 41a. In this case, the other container is preferably located upstream of the first container 410a.

[0062] Preferably, the protective agent 41b includes a first protective agent 41b1 capable of adsorbing water vapor and sulfur compounds, and a second protective agent 41b2 capable of adsorbing polycyclic aromatic compounds and tar. In this case, by using protective agents for the first protective agent 41b1 and the second protective agent 41b2 that differ in at least one of the following: average particle size, BET specific surface area, average pore diameter, density, temperature resistance, shape, etc., the adsorption and release capabilities for water vapor, sulfur compounds, polycyclic aromatic compounds, and tar can be suitably enhanced. Specifically, as shown in Figure 4, the first container 410a contains (arranges) the second protective agent 41b2, the first protective agent 41b1, and the first adsorbent 41a in order from the lower port 411a side (the side to which the raw material gas is supplied). With this configuration, the protective agent 41b adsorbs water vapor, sulfur compounds, polycyclic aromatic compounds, and tar before the raw material gas comes into contact with the first adsorbent 41a, so that the decrease in the activity of the first adsorbent 41a over time can be prevented or suppressed more reliably.

[0063] The first protective agent 41b1 and the second protective agent 41b2 can each be composed of the same substances as those listed for adsorbent 4a. Preferably, the first protective agent 41b1 is composed of zeolite, and the second protective agent 41b2 is composed of activated carbon. In this case, the first protective agent 41b1 can exhibit excellent adsorption capacity for water vapor and sulfur compounds, and the second protective agent 41b2 can exhibit excellent adsorption capacity for polycyclic aromatic compounds and tar. In this case, it is preferable that the first adsorbent 41a is composed of activated carbon with a larger pore size than the activated carbon that constitutes the second protective agent 41b2. This makes it possible to remove substances that adversely affect the first adsorbent 41a, so that the first adsorbent 41a can sufficiently and reliably adsorb and detach monocyclic aromatic compounds.

[0064] Preferably, a purge gas supply unit 43 for supplying purge gas is connected to at least one of the first container 410a and the second container 420a on the side opposite to where the raw material gas is supplied. In this embodiment, the purge gas supply unit 43 is connected to the upper port 412a of the first container 410a via gas line GL41, and to the upper port 422a of the second container 420a via gas line GL42 which is branched from gas line GL41. In addition, a valve V7 is provided in the middle of gas line GL41, and a valve V8 is provided in the middle of gas line GL42.

[0065] With this configuration, the first adsorbent 41a, the first protective agent 41b1, the second protective agent 41b2, and the second adsorbent 42a can be cleaned and regenerated by supplying purge gas to the first container 410a and the second container 420a while simultaneously reducing the pressure inside the first container 410a by the action of the pressure pump P2 and the second container 420a by the action of the pressure pump P3. The purge gas is as described above.

[0066] Furthermore, thermometers TE are connected to the first container 410a and the second container 420a, respectively. This makes it possible to measure the temperature inside the first container 410a and the temperature inside the second container 420a. Pressure gauges PT are connected to the lower port 411a and upper port 412a of the first container 410a, and to the lower port 421a and upper port 422a of the second container 420a, respectively. This makes it possible to measure the pressure of the gas supplied to and discharged from the first container 410a and the pressure of the gas supplied to and discharged from the second container 420a, respectively. A hygrometer AE is connected in the middle of the gas line GL12. This makes it possible to measure the humidity of the raw material gas passing through the gas line GL12.

[0067] Next, the method of using the manufacturing system 100 of the second embodiment (method of manufacturing valuable materials) will be described. [1] First, the raw material gas (raw material gas containing carbon monoxide, carbon dioxide and other gaseous components) discharged from the gasification furnace 10 is supplied to the filter device 3. At this time, minute solid particles (for example, tar, soot, etc.) contained in the raw material gas are removed.

[0068] [2] Next, valves V1, V2, V3, and V4 are opened, and valves V5, V6, V7, and V8 are closed, and the air supply pump P1 is activated. As a result, the raw material gas discharged from the filter device 3 passes through the first PSA device 41 (first container 410a). At this time, polycyclic aromatic compounds and tar are adsorbed by the second protective agent 41b2, and water vapor and sulfur compounds are adsorbed by the first protective agent 41b1. By removing these substances, the deterioration of the performance of the first adsorbent 41a over time can be suitably prevented or suppressed. After that, monocyclic aromatic compounds are adsorbed by the first adsorbent 41a.

[0069] [3] The raw material gas discharged from the first PSA device 41, from which monocyclic aromatic compounds and the like have been separated, then passes through the second PSA device 42 (second container 420a). At this time, carbon dioxide and the like are adsorbed by the second adsorbent 42a. [4] Next, the raw material gas discharged from the second PSA device 42 passes through the catalyst device 5. At this time, oxygen and acetylene are removed from the raw material gas. [5] After that, the raw material gas that has passed through the pre-treatment device is supplied to the culture tank 2. [6] Next, the organic substance-containing liquid obtained in the culture tank 2 is purified in the purification device 6.

[0070] [7] When a predetermined time has elapsed and the performance of the second protective agent 41b2, the first protective agent 41b1, and the first adsorbent 41a has deteriorated, valves V1 and V2 are closed, valve V5 is opened, and the pressure reducing pump P2 is activated. This releases and separates monocyclic aromatic compounds from the first adsorbent 41a, etc. in the first container 410a. As a result, off-gas containing monocyclic aromatic compounds, etc. can be recovered. At this time, valve V7 is opened and purge gas is supplied to the first container 410a from the purge gas supply unit 43. This increases the efficiency of releasing monocyclic aromatic compounds, etc. from the first adsorbent 41a, etc., and allows the first adsorbent 41a, etc. to be cleaned.

[0071] [8] Similarly, if the performance of the second adsorbent 42a deteriorates after a predetermined time has elapsed, valves V3 and V4 are closed, valve V6 is opened, and the pressure reducing pump P3 is activated. This releases and separates carbon dioxide and other substances from the second adsorbent 42a in the second container 420a. As a result, off-gas containing carbon dioxide and other substances can be recovered. At this time, valve V8 is opened and purge gas is supplied to the second container 420a from the purge gas supply unit 43. This increases the efficiency of releasing carbon dioxide and other substances from the second adsorbent 42a, and the second adsorbent 42a can also be cleaned.

[0072] With the above configuration, there is no need to heat the purge gas supplied to the first container 410 and the second container 420, thus contributing to a reduction in thermal energy. Furthermore, by appropriately setting the material, average particle size, BET specific surface area, average pore diameter, filling amount, and arrangement order of the first adsorbent 41a, the second adsorbent 42a, the first protective agent 41b1, and the second protective agent 41b2, it is possible to make the PSA device 4 more compact, reduce the pipe diameter of the connected piping, decrease the pump capacity, and ultimately make the manufacturing system 100 more compact. The manufacturing system 100 of this second embodiment also provides the same functions and effects as the manufacturing system 100 of the first embodiment.

[0073] <Third Embodiment> Next, a manufacturing system for valuable materials according to the third embodiment will be described. The manufacturing system for valuable materials according to the third embodiment will be described below, focusing on the differences from the manufacturing systems for valuable materials of the first and second embodiments, and similar matters will be omitted from the description. Figure 5 is a schematic diagram showing the configuration of the PSA device in the manufacturing system for valuable materials according to the third embodiment. In the manufacturing system 100 of the third embodiment, the configuration of the PSA device is different, but otherwise it is the same as the manufacturing system 100 of the second embodiment.

[0074] In this embodiment, the purge gas supply unit 43 is connected to the upper port 422a of the second container 420a via gas line GL 41. The lower port 421a of the second container 420a is connected to the upper port 412a of the first container 4120a via gas line GL 42. Valve V8 is provided in the middle of gas line GL 41, and valve V7 is provided in the middle of gas line GL 42. In this embodiment, the protective agent 41b is omitted in the first PSA device 41.

[0075] The manufacturing apparatus 1 of the third embodiment comprises a second PSA apparatus 42 and a first PSA apparatus 41 (a different PSA apparatus from the second PSA apparatus 42). The first PSA apparatus (the other PSA apparatus) 41 is located further from the culture tank (valuable material generation unit) than the second PSA apparatus 42, that is, closer to the gasification furnace (gas generation unit) 10 than the second PSA apparatus 42. The apparatus is configured to supply the purge gas (detached gas) after it has passed through the second PSA apparatus 42 to the first PSA apparatus (the other PSA apparatus) 41. The manufacturing system 100 of this third embodiment also provides the same operation and effects as the manufacturing systems 100 of the first and second embodiments described above. In particular, in the third embodiment, the purge gas does not need to be discarded after a single use, so its effective utilization can be achieved.

[0076] <Fourth Embodiment> Next, a manufacturing system for valuable materials according to the fourth embodiment will be described. The manufacturing system for valuable materials according to the fourth embodiment will be described below, focusing on the differences from the manufacturing systems for valuable materials of the first to third embodiments, and similar matters will be omitted from the description. Figure 6 is a schematic diagram showing the configuration of the PSA device in the manufacturing system for valuable materials according to the fourth embodiment. In the manufacturing system 100 of the fourth embodiment, the configuration of the PSA device is different, but otherwise it is the same as the manufacturing system 100 of the second embodiment.

[0077] The manufacturing system 100 shown in Figure 6 has a first PSA device 41 with two first containers 410a and a second PSA device 42 with two second containers 420a. The manufacturing system 100 of this fourth embodiment also provides the same functions and effects as the manufacturing systems 100 of the first to third embodiments. In particular, in the fourth embodiment, since there are two first containers 410a and two second containers 420a, when supplying purge gas to one of the two first containers 410a, raw material gas can be supplied to the other, and similarly, when supplying purge gas to one of the two second containers 420a, raw material gas can be supplied to the other. As a result, continuous operation is possible without stopping the manufacturing system 100.

[0078] Furthermore, in the fourth embodiment, a valve V410 is provided to connect the upper ports 412a of the two first containers 410a, and a valve V420 is provided to connect the upper ports 422a of the two second containers 420a. These valves V410 and V420 are pressure equalizing valves that reduce rapid pressure fluctuations and gas loss when the gas adsorption / desorption process is repeated between the two first containers 410a and between the two second containers 420a.

[0079] <Fifth Embodiment> Next, a manufacturing system for valuable materials according to the fifth embodiment will be described. The manufacturing system for valuable materials according to the fifth embodiment will be described below, focusing on the differences from the manufacturing systems for valuable materials of the first to fourth embodiments, and similar matters will be omitted from the description. Figure 7 is a schematic diagram showing the configuration of the PSA device in the manufacturing system for valuable materials according to the fifth embodiment.

[0080] In the fifth embodiment of the manufacturing system 100, the configuration of the PSA device is different, but otherwise it is the same as the manufacturing system 100 of the second embodiment. In the manufacturing system 100 shown in Figure 7, a first container 410a (first PSA device 41) and a second container 420a (second PSA device 42) are connected in series, and a single pressure reducing pump P3 installed in the middle of the gas line GL13 makes it possible to reduce the pressure inside the first container 410a and the second container 420a. In other words, in the fifth embodiment, a single pressure reducing pump P3 constitutes the pressure reducing mechanism.

[0081] The manufacturing system 100 of this fifth embodiment also provides the same functions and effects as the manufacturing systems 100 of the first to fourth embodiments. In particular, in the manufacturing system 100 of the fifth embodiment, by adjusting the switching timing of valves V1 and V7 and the switching timing of valves V9 and V10, the raw material gas from which unwanted gas components have been removed and the off-gas containing unwanted gas components can be separated and recovered using a single pressure reducing pump P3.

[0082] <Sixth Embodiment> Next, a manufacturing system for valuable materials according to the sixth embodiment will be described. The manufacturing system for valuable materials according to the sixth embodiment will be described below, focusing on the differences from the manufacturing systems for valuable materials of the first to fifth embodiments, and similar matters will be omitted from the description. Figure 8 is a schematic diagram showing the configuration of the PSA device in the manufacturing system for valuable materials according to the sixth embodiment. Figure 9 is a schematic diagram showing the configuration of the PSA device according to the sixth embodiment.

[0083] In the sixth embodiment of the manufacturing system 100, the configuration of the PSA device is different, but otherwise it is the same as the manufacturing system 100 of the fifth embodiment. The manufacturing system 100 shown in Figure 8 includes one container 400 having a lower port 4001 and an upper port 4002. As shown in Figure 9, a partition wall 4003 is placed in the middle of the longitudinal direction inside the container 400, dividing it into a first storage space 400a on the left and a second storage space 400b on the right. A first adsorbent 41a is placed in the first storage space 400a, and a second adsorbent 42a is placed in the second storage space 400b.

[0084] Therefore, in this embodiment, the left region of the container 400 constitutes the first PSA device 41, and the right region constitutes the second PSA device 42. A valve body 4004 is provided in the center of the partition wall 4003. This valve body 4004 opens in accordance with the pressure difference between the first containment space 400a and the second containment space 400b, allowing the two spaces 400a and 400b to communicate with each other. The valve body 4004 preferably has high heat resistance and can be made of, for example, a check valve or a duckbill valve. Alternatively, a filter may be placed instead of the valve body 4004.

[0085] Furthermore, a single pressure reducing pump P3 installed in the middle of the gas line GL13 allows for the reduction of pressure inside the container 400. In other words, in the sixth embodiment as well, a single pressure reducing pump P3 constitutes the pressure reduction mechanism. The manufacturing system 100 of this sixth embodiment also provides the same operation and effects as the manufacturing systems 100 of the first to fifth embodiments described above. In particular, in the manufacturing system 100 of the sixth embodiment, by adjusting the switching timing of valves V1 and V7 and the switching timing of valves V9 and V10, the raw material gas from which unwanted gas components have been removed and the off-gas containing unwanted gas components can be separated and recovered using a single pressure reducing pump P3.

[0086] The PSA apparatus described above allows for the efficient separation of predetermined gas components by reducing the amount of detached gas used for regeneration. Furthermore, the valuable material manufacturing apparatus and valuable material manufacturing system allow for the efficient and stable production of valuable materials while reducing the thermal energy used in pretreatment. In addition, power energy can be reduced by appropriately setting the composition of the adsorbent. In the above embodiment, the use of a pump as the pressure reduction mechanism was described as an example, but the pressure reduction mechanism is not limited to a pump. For example, it can be configured as a cooling device that can reduce the pressure inside the container by cooling any part of the manufacturing system 100 (manufacturing apparatus 1) to reduce the pressure. The kPaG mentioned above is a unit of gauge pressure, and gauge pressure is the value obtained by subtracting atmospheric pressure from absolute pressure. Furthermore, the apparatus may be provided in the following embodiments.

[0087] (1) A PSA apparatus capable of separating predetermined gas components, comprising an adsorbent for adsorbing the gas components and a container for containing the adsorbent, configured to supply the gas to be treated, containing the gas components, into the container under pressurized conditions, and then supply a release gas that separates the gas components from the adsorbent into the container while depressurizing the inside of the container, wherein in a graph plotting the pressure change inside the container over time, the area enclosed by the graph and the horizontal axis passing through a pressure of 0 kPaG while the gas to be treated is being supplied into the container is A, and the area enclosed by the graph and the horizontal axis while the release gas is being supplied into the container is B, and the apparatus is configured to satisfy the relationship that B / A is 5 or less.

[0088] (2) A PSA apparatus as described in (1) above, wherein the flow rate when supplying the detached gas into the container is 0.1% or more and 25% or less of the flow rate when supplying the gas to be treated into the container.

[0089] (3) A PSA apparatus as described in (1) or (2) above, wherein the time for supplying the detached gas into the container is 0.1 times or more and 1.5 times or less the time for supplying the gas to be treated into the container.

[0090] (4) A PSA apparatus according to any one of (1) to (3) above, wherein the pressure inside the container when the detached gas is supplied into the container is -100 kPaG or more.

[0091] (5) A PSA apparatus according to any one of (1) to (4) above, wherein the adsorbent is composed of zeolite.

[0092] (6) A PSA apparatus according to any one of (1) to (5) above, wherein the gas component includes at least carbon dioxide.

[0093] (7) A PSA apparatus according to any one of (1) to (6) above, wherein the detached gas includes at least one selected from the group consisting of nitrogen and inert gases.

[0094] (8) A PSA apparatus according to any one of (1) to (7) above, further comprising a cooling mechanism for cooling the adsorbent.

[0095] (9) A valuable material manufacturing apparatus comprising a PSA apparatus according to any one of (1) to (8) above, capable of separating at least carbon dioxide from a raw material gas containing carbon monoxide and carbon dioxide, and a valuable material production unit that supplies the raw material gas from which at least the carbon dioxide has been separated and generates a valuable material from the carbon monoxide contained in the raw material gas.

[0096] (10) A valuable material manufacturing apparatus as described in (9) above, further comprising another PSA apparatus different from the PSA apparatus, and configured to supply the detached gas after passing through the PSA apparatus to the other PSA apparatus.

[0097] (11) A valuable material manufacturing apparatus as described in (10) or (11) above, wherein the other PSA apparatus is located further away from the valuable material generation section than the PSA apparatus.

[0098] (12) A valuable material manufacturing apparatus according to any one of (9) to (11) above, wherein the valuable material production unit is configured to produce the valuable material using microorganisms.

[0099] (13) A valuable material manufacturing system comprising a gas generation unit that generates raw material gases containing carbon monoxide and carbon dioxide, and a valuable material manufacturing apparatus connected to the gas generation unit as described in (9) above. Of course, this is not limited to this.

[0100] As previously described, various embodiments of the present invention have been explained, but these are merely examples and do not limit the scope of the invention in any way. These novel embodiments can be implemented in various other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their variations are included in the scope and spirit of the invention, as well as in the claims of the invention and its equivalents.

[0101] For example, the PSA device, the valuable materials manufacturing device, and the valuable materials manufacturing system may each be a combination of any of the configurations of the first to sixth embodiments described above. Furthermore, the PSA device, the valuable materials manufacturing system, and the valuable materials manufacturing device may each have other optional additional configurations compared to the above embodiments, may be replaced with any configuration that performs a similar function, and some configurations may be omitted.

[0102] The following describes a simulation of the purification efficiency of the raw material gas. Figure 10 is a diagram showing the configuration of the PSA apparatus used in the simulation. As shown in Figure 10, the adsorption towers consist of two connected in series on the left and two connected in series on the right. First, each adsorption tower is fitted with a zeolite adsorbent (average particle size: 1.5 mm, BET specific surface area: 500-700 m²). ２ It was assumed that the container held a pore size of 9 Å (per g). The raw material gas was then supplied at a temperature of 15°C and a flow rate of 300 Nm. ３The adsorption tower was supplied with a certain amount of gas per hour, and the tower was maintained at a maximum pressure of 50 kPaG for 30 minutes. After 30 minutes, the pressure inside the tower was reduced to a predetermined minimum pressure, at which point pure nitrogen gas was supplied to the tower as a purge gas at a temperature of 25°C and a pressure of 0.19 MPaG.

[0103] Then, the following three cases were simulated to show the change in carbon dioxide concentration in the recovered gas that passed through the adsorption tower. Case 1: The minimum pressure during depressurization in the adsorption tower was set to -95 kPaG, and the purge time (time to maintain the minimum pressure) was set to 25 minutes, while the purge gas flow rate was varied. Case 2: The minimum pressure was set to -95 kPaG, and the purge gas flow rate was set to 30 Nm³. ３ The purge time was varied as a measure of time. Case 3: Purge gas flow rate was set to 30 Nm ３ The pressure during depressurization inside the adsorption tower was varied, with a 25-minute purge time.

[0104] Figure 11 is a graph showing the simulation results for Case 1. Figure 12 is a graph showing the simulation results for Case 2. Figure 13 is a graph showing the relationship between the change in total purge gas flow rate and the rate of reduction (relative value) of carbon dioxide contained in the recovered gas ((a) for Case 1, (b) for Case 2). Figure 14 is a graph showing the simulation results for Case 3. In this simulation, the rate of reduction of carbon dioxide is calculated from the concentration of carbon dioxide in the raw material gas (recovered gas) after passing through the adsorption tower and the concentration of carbon dioxide in the raw material gas before being supplied to the adsorption tower. The comparison of calculation results in this simulation was performed using AspenAdsorption software (manufactured by AspenTech).

[0105] As shown in Figure 11, when the reduction rate of carbon dioxide after flowing purge gas for 25 minutes is taken as 100%, the reduction rate of carbon dioxide contained in the raw gas is calculated using a conventional purge gas flow rate of 30 Nm ３ Purge gas flow rate less than / hour: 1 Nm ３ Over 40% per hour, 15 Nm ３It was found that the flow rate could be reduced by more than 85% per hour. Therefore, the purge gas flow rate can be reduced to 1 / 2 or 1 / 30 of the conventional rate. ３ In the case of / hour, B / A is 0.5, and 25 Nm ３ In the case of time, B / A is 0.5.

[0106] Furthermore, as shown in Figure 12, when the reduction rate of carbon dioxide after purging gas for 25 minutes is taken as 100%, it was found that the reduction rate of carbon dioxide contained in the raw gas can be reduced to more than 40% with a purge time of 8 minutes, which is shorter than the conventional purging time of 25 minutes, and to more than 85% with a purge time of 20 minutes. Therefore, the purge time can be shortened to 1 / 3 and 1 / 5 of the conventional time. Note that when the purge time is 8 minutes, the B / A is 1.5, and when it is 20 minutes, the B / A is 0.7. In addition, a comparison between Figure 13(a) and Figure 13(b) showed that reducing the purge gas flow rate reduces the total purge gas flow rate required to achieve the same level of carbon dioxide removal from the raw gas as reducing the purge time.

[0107] Furthermore, as shown in Figure 14, when the reduction rate of carbon dioxide after flowing purge gas for 25 minutes is taken as 100%, it was found that the reduction rate of carbon dioxide contained in the raw gas can be reduced to more than 40% at a pressure of -75 kPaG, which is higher than the conventional minimum pressure of -95 kPaG, and to about 80% at -85 kPaG. Note that when the minimum pressure is -75 kPaG, the B / A ratio is 0.8, and when it is -85 kPaG, the B / A ratio is 0.6.

[0108] 100: Valuable material manufacturing system, 10: Gasifier, 1: Valuable material manufacturing equipment, 2: Culture tank, 3: Filter device, 4: PSA device, 40: Container, 401: Lower port, 402: Upper port, 4a: Adsorbent, 41: First PSA device, 410a: First container, 411a: Lower port, 412a: Upper port, 41a: First adsorbent, 41b: Protective agent, 41b1: First protective agent, 41b2: Second protective agent, 42: Second PSA device, 420a: Second container, 421a: Lower port, 422a: Upper port, 42a: Second adsorbent, 43: Purge gas supply unit, 400: Container, 400a: First containment space, 400b: Second containment space, 4001: Lower port T: 4002: Upper port, 4003: Partition, 4004: Valve body, 5: Catalyst device, 6: Purification device, GL1: Gas line, GL11: Gas line, GL12: Gas line, GL13: Gas line, GL2: Gas line, GL3: Gas line, GL41: Gas line, GL42: Gas line, LL: Liquid line, P1: Air supply pump, P2: Pressure pump, P3: Pressure pump, V1: Valve, V2: Valve, V3: Valve, V4: Valve, V5: Valve, V6: Valve, V7: Valve, V8: Valve, V9: Valve, V10: Valve, V410: Valve, V420: Valve, AE: Hygrometer, PT: Pressure gauge, TE: Thermometer, G: Graph, A: Area, B: Area

Claims

1. A PSA apparatus capable of separating predetermined gas components, comprising an adsorbent for adsorbing the gas components and a container for containing the adsorbent, configured to supply the gas to be treated, containing the gas components, into the container under pressurized conditions, and then supply a release gas, which separates the gas components from the adsorbent, into the container while depressurizing the container, wherein, in a graph plotting the pressure change inside the container over time, the area enclosed by the graph and the horizontal axis passing through a pressure of 0 kPaG while the gas to be treated is being supplied into the container is defined as A, and the area enclosed by the graph and the horizontal axis while the release gas is being supplied into the container is defined as B, the PSA apparatus is configured to satisfy the relationship that B / A is 5 or less.

2. A PSA apparatus according to claim 1, wherein the flow rate when supplying the detached gas into the container is 0.1% or more and 25% or less of the flow rate when supplying the gas to be treated into the container.

3. A PSA apparatus according to claim 1 or claim 2, wherein the time for supplying the detached gas into the container is 0.1 times or more and 1.5 times or less for supplying the gas to be treated into the container.

4. A PSA apparatus according to any one of claims 1 to 3, wherein the pressure inside the container when the detached gas is supplied into the container is -100 kPaG or more.

5. A PSA apparatus according to any one of claims 1 to 4, wherein the adsorbent is composed of zeolite.

6. A PSA apparatus according to any one of claims 1 to 5, wherein the gas component includes at least carbon dioxide.

7. A PSA apparatus according to any one of claims 1 to 6, wherein the detached gas includes at least one selected from the group consisting of nitrogen and inert gases.

8. A PSA apparatus according to any one of claims 1 to 7, further comprising a cooling mechanism for cooling the adsorbent.

9. A valuable material manufacturing apparatus comprising: a PSA apparatus according to any one of claims 1 to 8 capable of separating at least carbon dioxide from a raw material gas containing carbon monoxide and carbon dioxide; and a valuable material production unit that supplies the raw material gas from which at least carbon dioxide has been separated and generates a valuable material from the carbon monoxide contained in the raw material gas.

10. A valuable material manufacturing apparatus according to claim 9, further comprising another PSA apparatus different from the PSA apparatus, and configured to supply the detached gas after passing through the PSA apparatus to the other PSA apparatus.

11. A valuable material manufacturing apparatus according to claim 10 or claim 11, wherein the other PSA apparatus is located further away from the valuable material generating section than the PSA apparatus.

12. A valuable material manufacturing apparatus according to any one of claims 9 to 11, wherein the valuable material production unit is configured to produce the valuable material using microorganisms.

13. A valuable material manufacturing system comprising a gas generation unit that generates a raw material gas containing carbon monoxide and carbon dioxide, and a valuable material manufacturing apparatus connected to the gas generation unit as described in claim 9.

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