WO2023214564A1

WO2023214564A1 - Device, system, and method for producing carbonous valuable substance and carbonous material

Info

Publication number: WO2023214564A1
Application number: PCT/JP2023/017051
Authority: WO
Inventors: アルツゲラシカダサナヤケ; 宣利柳橋; 圭祐飯島; 友樹中間
Original assignee: 積水化学工業株式会社
Priority date: 2022-05-02
Filing date: 2023-05-01
Publication date: 2023-11-09

Abstract

[Problem] To provide a production device and the like for improving use efficiency of carbon monoxide, by generating a carbonous valuable substance from carbon monoxide and then converting unreacted carbon monoxide into a carbonous material. [Solution] According to one aspect of the present invention, provided is a device for producing a carbonous valuable substance and a carbonous material. The device is provided with: a first reaction unit for generating carbon monoxide from carbon dioxide; a second reaction unit for generating a carbonous valuable substance from carbon monoxide; and a third reaction unit for generating a carbonous material from unreacted carbon monoxide discharged from the second reaction unit.

Description

Manufacturing equipment, manufacturing system and manufacturing method

The present invention relates to a manufacturing device, a manufacturing system, and a manufacturing method.

In recent years, the concentration of carbon dioxide (CO ₂ ), a type of greenhouse gas, in the atmosphere has continued to rise. Rising concentrations of carbon dioxide in the atmosphere contribute to global warming. Therefore, it is important to recover carbon dioxide released into the atmosphere, and if the recovered carbon dioxide can be converted into valuable carbon materials and reused, a carbon recycling society can be realized.
In addition, as a global measure, as stated in the Kyoto Protocol of the United Nations Framework Convention on Climate Change, the reduction rate of carbon dioxide, which is the cause of global warming, in developed countries is set for each country based on 1990. It is stipulated that the reduction targets will be jointly achieved within the commitment period.

In order to achieve this reduction target, exhaust gases containing carbon dioxide generated from steel mills, smelters, and thermal power plants are also targeted, and various technological improvements have been made to reduce carbon dioxide emissions in these industries. ing. An example of such technology is CO ₂ capture and storage (CCS). However, this technology has the physical limit of storage and is not a fundamental solution.
In addition, for example, Patent Document 1 discloses a carbon dioxide reduction system that produces carbon monoxide from carbon dioxide. This carbon dioxide reduction system includes a combustion furnace that generates exhaust gas containing carbon dioxide, a carbon dioxide separation device that separates carbon dioxide from the exhaust gas, and a reduction device that reduces the separated carbon dioxide to carbon monoxide. We are prepared.

International Publication No. 2019/163968

However, when converting carbon monoxide into carbon valuables, it is necessary to strictly control the ratio of carbon monoxide to hydrogen. In addition, since it is difficult to achieve a 100% conversion rate of carbon monoxide to carbon valuables, unreacted carbon monoxide must be disposed of after the conversion reaction of carbon monoxide to carbon valuables. Become. In contrast, the conversion of carbon monoxide to a carbon material does not require strict control of the reaction.
In view of the above-mentioned circumstances, the present invention provides a manufacturing device that improves the utilization efficiency of carbon monoxide by converting unreacted carbon monoxide into carbon materials after generating carbon valuables from carbon monoxide. We decided to provide the following.

According to one aspect of the present invention, an apparatus for producing carbon valuables and carbon materials is provided. This device includes a first reaction section that produces carbon monoxide from carbon dioxide, a second reaction section that produces carbon valuables from carbon monoxide, and unreacted water discharged from the second reaction section. and a third reaction section that generates a carbon material from carbon oxide.

According to this embodiment, carbon valuables and carbon materials can be produced while improving the utilization efficiency of carbon monoxide.

1 is a schematic diagram showing the configuration of a first embodiment of a manufacturing system of the present invention. FIG. 2 is a schematic diagram showing the configuration of a first reactor in the first embodiment. It is a schematic diagram showing the composition of a 2nd embodiment of the manufacturing system of the present invention. It is a schematic diagram showing the composition of a 3rd embodiment of the manufacturing system of the present invention. It is a schematic diagram showing the composition of the 1st reaction part in a 4th embodiment.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The manufacturing apparatus, manufacturing system, and manufacturing method of the present invention will be described in detail below based on preferred embodiments shown in the accompanying drawings.
<<First embodiment>>
First, a first embodiment of the manufacturing system of the present invention will be described.
FIG. 1 is a schematic diagram showing the configuration of a first embodiment of the manufacturing system of the present invention. FIG. 2 is a schematic diagram showing the configuration of the first reactor in the first embodiment.

The manufacturing system 10 shown in FIG. 1 includes a manufacturing device 100 (hereinafter also simply referred to as the “manufacturing device 100”) that manufactures carbon valuables and carbon materials, and is connected to the manufacturing device 100 and includes exhaust gas (a raw material containing carbon dioxide). The blast furnace (gas supply section) 1 supplies a gas) and a reducing gas supply section 2 supplies a reducing gas.
Note that, in this specification, the upstream side with respect to the gas flow direction is also simply referred to as "upstream side," and the downstream side is also simply referred to as "downstream side." Furthermore, in this specification, "smelting" also includes "refining" performed to increase the purity of metal.

In this embodiment, the gas supply section will be described as a blast furnace (furnace related to a smelter) 1, but the gas supply section may be another furnace related to a smelter. Other preferable furnaces include shaft furnaces, converter furnaces, electric furnaces, and the like. Further, the gas supply unit may be a CO _x emission source of at least one business facility selected from a garbage incinerator, a paper factory, a cement factory, a thermal power plant, an oil refinery, an ethylene cracker, an oil refinery, and a chemical factory. . In each furnace, exhaust gas containing carbon dioxide is generated during combustion, melting, refining, etc. of the contents.
In the case of a combustion furnace (incinerator) at a garbage incinerator, the contents (waste) include, for example, plastic waste, food garbage, municipal waste (MSW), waste tires, biomass waste, household garbage (bedding), etc. , paper), construction materials, etc. Note that these wastes may contain one type alone or two or more types.

In addition to carbon dioxide and carbon monoxide, exhaust gas typically contains other gas components such as nitrogen, oxygen, water vapor, and methane. The concentration of carbon dioxide contained in the exhaust gas is not particularly limited, but in consideration of the production cost of the generated gas (conversion efficiency into carbon material), it is preferably 1% by volume or more, more preferably 5% by volume or more.
In the case of exhaust gas from a combustion furnace at a garbage incinerator, carbon dioxide is 5% to 15% by volume, nitrogen is 60% to 70% by volume, oxygen is 5% to 10% by volume, and water vapor is 15% by volume. It is contained in an amount of not less than 25% by volume.

The exhaust gas (blast furnace gas) from the blast furnace 1 is, for example, gas generated when producing pig iron in the blast furnace 1, and contains carbon dioxide of 5% to 45% by volume and nitrogen of 55% to 60% by volume. , carbon monoxide is contained in an amount of 10 volume % or more and 40 volume % or less, and hydrogen is contained in an amount of 1 volume % or more and 10 volume % or less.
In addition, exhaust gas from a converter (converter gas) is a gas generated when manufacturing steel in a converter, and contains carbon dioxide of 15% to 20% by volume and carbon monoxide of 50% to 80% by volume. Nitrogen is contained in an amount of 15% to 25% by volume, and hydrogen is contained in an amount of 1% to 5% by volume.
Note that pure gas containing 100% by volume of carbon dioxide may be used as the exhaust gas.

However, if exhaust gas is used, the carbon dioxide that was conventionally emitted into the atmosphere can be effectively used, and the burden on the environment can be reduced. Among these, from the viewpoint of carbon circulation, exhaust gas containing carbon dioxide generated in a smelter is preferable.
Further, as the blast furnace gas and converter gas, untreated gas discharged from the furnace may be used as is, for example, treated gas after being subjected to treatment to remove carbon monoxide, etc. (described later). may be used. The untreated blast furnace gas and the converter gas each have the gas compositions described above, and the treated gas has a gas composition close to that of the exhaust gas from the combustion furnace. In this specification, all of the above gases (gases before being supplied to the manufacturing apparatus 100) are referred to as exhaust gas.

The reducing gas supply unit 2 is configured with, for example, a hydrogen generator that generates hydrogen by electrolyzing water. A tank storing water is connected to this hydrogen generator.
According to the hydrogen generator, a large amount of hydrogen can be generated relatively inexpensively and easily. Another advantage is that condensed water generated within the manufacturing apparatus 100 can be reused. Note that since the hydrogen generator consumes a large amount of electrical energy, it is effective to use electricity as renewable energy.
As renewable energy, electrical energy using at least one selected from solar power generation, wind power generation, hydropower generation, wave power generation, tidal power generation, biomass power generation, geothermal power generation, solar heat, and geothermal heat is used. It is possible.

Note that a device that generates by-product hydrogen can also be used as the hydrogen generator. Examples of devices that generate by-product hydrogen include devices that electrolyze an aqueous sodium chloride solution, devices that steam-reform petroleum, and devices that produce ammonia.
Further, the reducing gas supply section 2 can also be a coke oven. In this case, exhaust gas from the coke oven may be used as the reducing gas. This is because the exhaust gas from the coke oven has hydrogen and methane as its main components, and contains hydrogen in an amount of 50% by volume or more and 60% by volume or less.

The manufacturing apparatus 100 of this embodiment is an apparatus for manufacturing carbon valuables and carbon materials, and includes a gas switching section 3, two first reactors 4a and 4b (first reaction section 4), and one It includes a second reactor (second reaction section) 5 and one third reactor (third reaction section) 6.
Blast furnace (blast furnace) 1 is connected to gas switching section 3 via gas line GL1, and reducing gas supply section 2 is connected to gas switching section 3 via gas line GL2.
In the middle of each gas line GL1, GL2, at least one of a temperature control section that adjusts the temperature of the gas passing through it, a pressurization section that pressurizes the gas, an impurity removal section that removes impurities from the gas, etc. is arranged. You may also do so.
The gas switching unit 3 can be configured to include, for example, a branch gas line and a passage opening/closing mechanism such as a valve provided in the middle of the branch gas line.

The gas switching unit 3 is connected to the inlet ports of the first reactors 4a, 4b via two gas lines GL3a, GL3b, respectively.
With this configuration, the exhaust gas (raw material gas containing carbon dioxide) supplied from the blast furnace 1 passes through the gas line GL1, the gas switching unit 3, and the gas lines GL3a and GL3b, and is then delivered to each of the first reactors 4a and 4b. Supplied.
On the other hand, the reducing gas containing hydrogen (reducing substance) supplied from the reducing gas supply section 2 passes through the gas line GL2, the gas switching section 3, and the gas lines GL3a and GL3b, and is supplied to each of the first reactors 4a and 4b. supplied to

The first reactors 4a and 4b are capable of producing carbon monoxide from carbon dioxide (capable of converting carbon dioxide into linear carbon). As shown in FIG. 2, each of the first reactors 4a and 4b includes a plurality of tube bodies 41 each filled with (accommodating) a reducing agent (reductant) 4R, and a plurality of tube bodies 41 housed in an internal space 43. The reactor is a multi-tubular reactor (fixed bed reactor) having a housing 42 with a cylindrical structure. According to such a multi-tubular reactor, a sufficient opportunity for contact between the reducing agent 4R and the exhaust gas and the reducing gas can be ensured. As a result, the conversion efficiency of carbon dioxide into carbon monoxide can be increased.
Note that the first reactors 4a and 4b may be configured by omitting the tube 41 and filling the internal space 43 of the housing 42 with the reducing agent 4R (ie, a simple reactor).
The reducing agent 4R of this embodiment is preferably in the form of particles, scales, pellets, etc., for example. If the reducing agent 4R has such a shape, it is possible to increase the filling efficiency into the pipe body 41 and further increase the contact area with the gas supplied into the pipe body 41.

When the reducing agent 4R is in the form of particles, its volume average particle diameter is not particularly limited, but is preferably 1 mm or more and 50 mm or less, and more preferably 1 mm or more and 30 mm or less. In this case, the contact area between the reducing agent 4R and the exhaust gas (carbon dioxide) can be further increased, and the conversion efficiency of carbon dioxide into carbon monoxide can be further improved. Similarly, regeneration (reduction) of the reducing agent 4R using a reducing gas containing a reducing substance can be performed more efficiently.
The particulate reducing agent 4R is preferably a molded body manufactured by rolling granulation because the sphericity is further increased.

Further, the reducing agent 4R may be supported on a carrier.
The constituent material of the carrier may be any material that is difficult to modify due to contact with exhaust gas (oxidizing gas) or reaction conditions, such as carbon materials (graphite, graphene, carbon black, carbon nanotubes, activated carbon, etc.), Mo ₂ C, etc. Examples include carbides such as zeolite, montmorillonite, oxides such as ZrO ₂ , TiO ₂ , V ₂ O ₅ , MgO, CeO ₂ , Al ₂ O ₃ , SiO _{2 ,} and composite oxides containing these.

Among these, zeolite, montmorillonite, ZrO ₂ , TiO ₂ , V ₂ O ₅ , MgO, Al ₂ O ₃ , SiO ₂ and composite oxides containing these are preferable as constituent materials of the carrier. A carrier made of such a material is preferable because it does not adversely affect the reaction of the reducing agent 4R and has an excellent ability to support the reducing agent 4R. Here, the carrier does not participate in the reaction of the reducing agent 4R and simply supports (holds) the reducing agent 4R.
An example of such a configuration is a configuration in which at least a portion of the surface of the carrier is coated with the reducing agent 4R.

The reducing agent 4R contains at least one of a metal and a metal oxide (oxygen carrier with oxygen ion conductivity). At least one of the metal and the metal oxide preferably contains at least one metal element selected from Groups 3 to 13, although it is not particularly limited as long as it can reduce carbon dioxide. It is more preferable to contain at least one metal element selected from metal elements belonging to Groups 3 to 12, such as lanthanum, titanium, vanadium, iron, copper, zinc, nickel, manganese, chromium, and cerium. It is more preferable to contain seeds, and metal oxides or composite metal oxides containing iron and/or cerium are particularly preferable. These metal oxides are useful because they have particularly good efficiency in converting carbon dioxide to carbon monoxide.
Here, the metal includes a simple metal consisting of only one of the above metal elements, and an alloy consisting of two or more of the above metal elements.

Furthermore, in each of the first reactors 4a and 4b, the tube body (cylindrical molded body) 41 may be made of the reducing agent 4R (at least one of a metal and a metal oxide) itself. Furthermore, a block-shaped, lattice-shaped (for example, net-shaped, honeycomb-shaped) molded body may be produced using the reducing agent 4R, and the molded body may be placed in the housing 42. In these cases, the reducing agent 4R as a filler may be omitted or may be used in combination.

Among these, a configuration in which a net-like body is produced using the reducing agent 4R and placed inside the housing 42 is preferable. In the case of such a configuration, sufficient opportunity for contact between the reducing agent 4R and the exhaust gas and reducing gas is ensured while preventing the passage resistance of the exhaust gas and reducing gas from increasing in each of the first reactors 4a and 4b. You can also do it.
The volumes of the two first reactors 4a and 4b are set to be approximately equal to each other, and are appropriately set depending on the amount of exhaust gas to be treated (the size of the blast furnace 1 and the size of the manufacturing apparatus 100). Further, the volumes of the two first reactors 4a and 4b may be varied depending on the types of exhaust gas and reducing gas, the performance of the reducing agent 4R, and the like.

According to the above configuration, by switching the gas line (flow path) in the gas switching unit 3, for example, the reducing agent 4R before oxidation is connected to the first reactor 4a containing the reducing agent 4R via the gas line GL3a. The exhaust gas can be supplied via the gas line GL3b to the first reactor 4b containing the oxidized reducing agent 4R. At this time, a reaction expressed by the following formula 1 proceeds in the first reactor 4a, and a reaction expressed by the following formula 2 proceeds in the first reactor 4b.

Note that in the following formulas 1 and 2, the case where the reducing agent 4R contains iron oxide (FeO _x-1 ) is shown as an example.
Formula 1: CO ₂ + FeO _x−1 → CO + FeO _x
Formula 2: H ₂ + FeO _x → H ₂ O + FeO _x-1
Thereafter, by switching the gas line in the opposite direction to the above in the gas switching unit 3, the reaction of the above formula 2 is allowed to proceed in the first reactor 4a, and the reaction of the above formula 1 is allowed to proceed in the first reactor 4b. I can do it.
That is, exhaust gas and reducing gas are switched and supplied to the first reactor 4a and the first reactor 4b.

Note that the reactions shown in Formulas 1 and 2 above are both endothermic reactions. For this reason, the manufacturing system 10 includes a reducing agent heating unit ( (not shown in FIG. 1).
By providing such a reducing agent heating section, the temperature during the reaction between the exhaust gas or reducing gas and the reducing agent 4R is maintained at a high temperature, and a decrease in the conversion efficiency of carbon dioxide to carbon monoxide is suitably prevented or suppressed. , the regeneration of the reducing agent 4R by the reducing gas can be further promoted.

However, depending on the type of reducing agent 4R, the reactions shown in Formulas 1 and 2 above may become exothermic reactions. In this case, the manufacturing system 10 preferably includes a reducing agent cooling section that cools the reducing agent 4R instead of the reducing agent heating section. By providing such a reducing agent cooling section, deterioration of the reducing agent 4R is suitably prevented during the reaction between the exhaust gas or reducing gas and the reducing agent 4R, and the conversion efficiency of carbon dioxide into carbon monoxide is improved. It is possible to suitably prevent or suppress the decrease, and further promote the regeneration of the reducing agent 4R by the reducing gas.
That is, the manufacturing system 10 is preferably provided with a reducing agent temperature control section that adjusts the temperature of the reducing agent 4R depending on the type of reducing agent 4R (exothermic reaction or endothermic reaction).

Here, the conversion rate of carbon dioxide to carbon monoxide in the first reactors 4a, 4b is preferably 70% or more, more preferably 85% or more, and preferably 95% or more. More preferred. The upper limit of the conversion rate of carbon dioxide to carbon monoxide is usually about 98%.
Such a conversion rate depends on the type of reducing agent 4R used, the concentration of carbon dioxide contained in the exhaust gas, the type of reducing substance, the concentration of reducing substance contained in the reducing gas, the temperature of the first reactors 4a and 4b, It can be set by adjusting the flow rate (flow rate) of exhaust gas and reducing gas to the first reactors 4a, 4b, the timing of switching between exhaust gas and reducing gas, etc.

Gas lines GL4a and GL4b are connected to the outlet ports of the first reactors 4a and 4b, respectively, and these meet at a gas merging section J to form a gas line GL4. Additionally, valves (not shown) are provided in the middle of the gas lines GL4a and GL4b, as necessary.
For example, by adjusting the opening degree of the valve, the passing rate of the exhaust gas and reducing gas passing through the first reactors 4a and 4b (i.e., the processing rate of the exhaust gas by the reducing agent 4R and the processing rate of the reducing agent 4R by the reducing gas) can be adjusted. speed) can be set.

Gas line GL4 is connected to the inlet port of second reactor 5. That is, the second reactor (second reaction section) 5 is connected to the first reactors 4a, 4b (first reaction section) via gas lines GL4a, GL4b and gas line GL4. . Thereby, the exhaust gas from the first reactors 4a, 4b can be supplied to the second reactor 5 as a mixed gas.
The second reactor 5 is capable of producing carbon valuables from carbon monoxide (capable of converting carbon monoxide into carbon valuables). Specifically, in the second reactor 5, an olefin compound, which is a type of carbon valuable substance, is produced from carbon monoxide and hydrogen contained in the mixed gas. That is, in the second reactor 5, a so-called Fischer-Tropsch reaction is performed.
As the second reactor 5, a reactor similar to that described for the first reactors 4a, 4b can be used. In this case, the tube body 41 is filled with a catalyst containing at least one of iron, cobalt, ruthenium, nickel, molybdenum, aluminum, and silicon, for example.

Here, examples of the olefin compound include ethylene, propylene, butene, butadiene, etc., and one or more of these may be used. Among these, it is preferable that the olefin compound contains ethylene. This is because olefin compounds containing ethylene are useful as raw materials for various industrial products.
Note that by changing the type of catalyst, the second reactor 5 can generate other carbon valuables other than olefin compounds from the carbon monoxide and hydrogen contained in the mixed gas. Examples of other carbon valuables include oxygen-containing compounds, aromatic compounds, and the like.

Examples of the oxygen-containing compound include methanol, ethanol, acetaldehyde, acetone, and butanol, and one or more of these may be used. Among these, the oxygen-containing compound preferably contains methanol. This is because oxygen-containing compounds containing methanol are useful as raw materials for various industrial products.
In this case, usable catalysts include, for example, catalysts containing at least one of titanium, copper, silver, zinc, rhodium, manganese, nickel, aluminum, and silicon.

On the other hand, examples of the aromatic compound include benzene, toluene, xylene, etc., and one or more of these may be used. Among them, it is preferable that the aromatic compound contains toluene. This is because aromatic compounds containing toluene are useful as raw materials for various industrial products.
In this case, examples of catalysts that can be used include catalysts containing at least one of molybdenum, tungsten, rhenium, nickel, aluminum, and silicon.
Note that the catalyst may be a supported catalyst, a composite oxide such as zeolite, or a composite oxide supporting a metal.

Alternatively, a continuous method may be adopted in which the exhaust gas and reducing gas discharged from the first reactors 4a and 4b are continuously supplied to the second reactor 5 at the same timing without being combined. It is also possible to adopt a batch method in which only the exhaust gas is supplied (sealed) with the outlet port of the second reactor 5 closed, then the reducing gas is supplied, and then the outlet port of the second reactor 5 is opened. . It is also possible to adopt a method in which two second reactors 5 are provided and exhaust gas and reducing gas are alternately supplied to each of them.

The first reaction temperature in the first reactors 4a, 4b (first reaction section 4) is preferably higher than the second reaction temperature in the second reactor (second reaction section) 5. In this case, the reaction heat in the first reactors 4a, 4b can be effectively used in the second reactor 5.
Specifically, the difference between the first reaction temperature and the second reaction temperature is preferably 100°C or more, more preferably 150°C or more and 500°C or less, and 200°C or more and 400°C or less. It is even more preferable that there be. Thereby, while improving the reaction efficiency in the first reactors 4a, 4b and the second reactor 5, it is also possible to improve the heat utilization efficiency.
The reaction temperature of the second reactor 5 is preferably 100°C or more and 400°C or less, more preferably 150°C or more and 350°C or less, and even more preferably 200°C or more and 300°C or less. .

The first reaction pressure in the first reactors 4a, 4b (first reaction section 4) is preferably lower than the second reaction pressure in the second reactor (second reaction section) 5. In this case, gas (exhaust gas, reducing gas, and mixed gas) can be supplied to the second reactor 5 from the front stage of the first reactors 4a and 4b without repeating pressure increase and decrease. That is, since the pressure of the gas can be increased stepwise (efficiently), energy utilization efficiency can be increased.
The second reaction pressure is preferably more than 1 MPaG, more preferably 1.5 MPaG or more and 5 MPaG or less, and even more preferably 2 MPaG or more and 4 MPaG or less. Thereby, the reaction efficiency in the second reactor 5 can be further improved.

A gas component removing section 12 is arranged in the middle of the gas line GL4. This gas component removal section 12 removes gas components having a boiling point higher than the boiling point of CO from the exhaust gas from the first reactors 4a, 4b. By removing such gas components (impurity gas components), the components that inhibit the reaction in the second reactor 5 are reduced, and the efficiency can be further improved.
In this embodiment, examples of gas components include H ₂ O, CO ₂ , methane, ethane, methanol, ethanol, ethylene oxide, propylene oxide, and the like.

The gas component removal unit 12 may be configured with a cooler that cools the exhaust gas (mixed gas) from the first reactors 4a and 4b, and increases the pressure of the exhaust gas to convert it into a gas having a boiling point higher than the boiling point of CO. It may be configured with a condenser that liquefies the components, a separation membrane that allows the passage of molecules to be reacted in the second reactor 5 and blocks the passage of other molecules, or a separation membrane that allows the passage of molecules to be reacted in the second reactor 5, or It may be composed of a separation membrane that blocks the passage of molecules to be reacted and allows the passage of other molecules, or it may be composed of any or all combinations of a cooler, a condenser, and a separation membrane. .
As the cooler, a cooler having a configuration similar to that described below can be used.
On the other hand, the condenser may include a compressor for increasing the pressure and a gas-liquid separator.
On the other hand, the separation membrane can be made of a metal, an inorganic oxide, or a metal organic framework (Metal Organic FRAM (registered trademark) eworks: MOF).

Here, examples of the metal include titanium, aluminum, copper, nickel, chromium, cobalt, and alloys containing these. When using metal, the separation membrane is preferably a porous body with a porosity of 80% or more.
Examples of the inorganic oxide include silica and zeolite.
Further, examples of the metal-organic structure include a structure of zinc nitrate hydrate and terephthalate dianion, a structure of copper nitrate hydrate and trimesate trianion, and the like.

It is preferable that the separation membrane is composed of a porous body having continuous pores (pores penetrating the cylindrical wall) in which adjacent pores communicate with each other. With a separation membrane having such a configuration, the permeability of H ₂ O or CO can be increased, and the separation between H ₂ O and H ₂ and/or the separation between CO and CO ₂ can be performed more smoothly and reliably. .
The porosity of the separation membrane is not particularly limited, but is preferably 10% or more and 90% or less, more preferably 20% or more and 60% or less. This makes it possible to maintain a sufficiently high permeability of H ₂ O or CO while preventing the mechanical strength of the separation membrane from decreasing excessively.
Note that the shape of the separation membrane is not particularly limited, and examples thereof include a cylindrical shape, a quadrangular shape, a rectangular tube shape such as a hexagonal shape, and the like.

From the viewpoint of further increasing the conversion efficiency of carbon dioxide into carbon monoxide, it is effective to increase the reduction (regeneration) efficiency of the reducing agent 4R in an oxidized state.
In this case, the average pore diameter of the separation membrane is preferably 600 pm or less, more preferably 400 pm or more and 500 pm or less. Thereby, the separation efficiency between H ₂ O and H ₂ can be further improved.
Note that the separation membrane is normally used while being housed in a housing. In this case, the pressure in the space outside the separation membrane within the housing may be reduced or a carrier gas (sweep gas) may be allowed to pass therethrough. Examples of the carrier gas include helium, inert gas such as argon, and the like.

Further, the separation membrane is preferably hydrophilic. If the separation membrane has hydrophilicity, the affinity of water for the separation membrane will increase, and H ₂ O will more easily permeate through the separation membrane.
Methods of imparting hydrophilicity to a separation membrane include methods of improving the polarity of the separation membrane by changing the ratio of metal elements in the inorganic oxide (for example, increasing the Al/Si ratio); Examples include a method of coating the separation membrane with a polymer, a method of treating the separation membrane with a coupling agent having a hydrophilic group (polar group), and a method of subjecting the separation membrane to plasma treatment, corona discharge treatment, etc.
Furthermore, the affinity for water may be controlled by adjusting the surface potential of the separation membrane.

On the other hand, when separating CO and CO ₂ with priority in a separation membrane, or when separating both H ₂ O and H ₂ and separating CO and CO ₂ at the same time, the configuration of the separation membrane is The material, porosity, average pore diameter, degree of hydrophilicity or hydrophobicity, surface potential, etc. may be appropriately combined and set.
It is also possible to configure the tube bodies 41 of the first reactors 4a, 4b with such separation membranes, but in this case, the separation membranes deteriorate due to heat, so the temperature of the first reactors 4a, 4b (reaction temperature ) cannot be set to a high temperature.
On the other hand, by arranging the separation membrane outside the first reactors 4a, 4b, the temperature of the first reactors 4a, 4b can be set to a relatively high temperature, and therefore, the temperature of the first reactors 4a, 4b can be set to a relatively high temperature. The conversion efficiency to carbon oxide and the regeneration (reduction) efficiency of the reducing agent 4R by the reducing gas can be further improved.

The mixed gas (exhaust gas) of exhaust gas and reducing gas that has passed through the gas component removal section 12 is supplied to the second reactor 5 . That is, unreacted hydrogen (reducing substance) with the reducing agent 4R (at least one of metal and metal oxide) in the first reactors 4a and 4b is converted into carbon valuables such as carbon monoxide in the second reactor 5. is configured for use in converting to .
In this way, by reusing unreacted hydrogen (reducing substance), waste of raw materials can be reduced.

A gas line GL5 is connected to the outlet port of the second reactor 5. This gas line GL5 is connected to the inlet port of the third reactor 6. That is, the third reactor (third reaction section) 6 is connected to the second reactor (second reaction section) 4 via the gas line GL5. Thereby, the exhaust gas from the second reactor 5 can be supplied to the third reactor 6.
The third reactor 6 is capable of generating (converting) carbon material from unreacted carbon monoxide discharged from the second reactor 5. Specifically, in the third reactor 6, a carbon material is generated from carbon monoxide contained in the mixed gas (exhaust gas) by a so-called boudoir reaction shown in the following equation 3.
Formula 3: 2CO ⇔ C + CO ₂
As the third reactor 6, a reactor similar to that described for the first reactors 4a, 4b can be used. In this case, the tube body 41 is filled with, for example, rhodium, nickel, cerium, platinum, or one or more of the following catalysts. Examples of the catalyst include (1) tungsten, rhenium, osmium, tantalum, molybdenum, niobium, iridium, ruthenium, hafnium, technetium, rhodium, vanadium, chromium, zirconium, platinum, thorium, lutetium, titanium, palladium, protactinium, Thulium, scandium, iron, yttrium, erbium, cobalt, holmium, nickel, dysprosium, terbium, curium, cadrinium, beryllium, manganese, americium, promethium, uranium, copper, samarium, gold, actinium, neodymium, bercurium, silver, germanium, praseodymium, lanthanum, californium, calcium, europium, ytterbium, cerium, strontium, barium, radium, aluminum, magnesium, plutonium, neptinium, antimony, zinc, lead, cadmium, thallium, bismuth, polonium, tin, lithium, indium, sodium, Elements (single elements or complexes) containing potassium, rubidium, gallium, cesium, silicon or tellurium; (2) sulfides, borides, oxides, chlorides, hydroxides, nitrides and organometallic compounds of the above elements; , (3) A mixture of either (1) or (2) above and sulfur and/or sulfide (including organic sulfur compounds), (4) A mixture of either (1) or (2) above and boron and /or a mixture with a boride (including an organic boron compound), etc.

A first recovery section 7 for recovering carbon valuables and a pressure adjustment section 8 for increasing the pressure of the mixed gas passing through the gas line GL5 are provided in the middle of the gas line GL5.
The first recovery section 7 can be composed of, for example, a separation tower, an absorption tower, or the like.
Furthermore, by increasing the pressure of the mixed gas (the gas after passing through the first recovery section 7) using the pressure adjustment section 8, the equilibrium of the reaction described in Equation 3 can be shifted (tilted) to the right, Therefore, the production efficiency of carbon material can be further improved.
Specifically, the pressure of the mixed gas after pressurization by the pressure regulator 8 is preferably 0.1 MPaG or more, more preferably 0.1 MPaG or more and 10 MPaG or less, and 0.1 MPaG or more and 5 MPaG or less. It is more preferably 0.1 MPaG or more and 3 MPaG or less, most preferably 0.1 MPaG or more and 2 MPaG or less. Note that the lower limit of the pressure may be 0.2 MPaG or more, or 0.5 MPaG or more. By adjusting the pressure of the mixed gas, the production efficiency of carbon material can be further increased.
The pressure adjustment section 8 can be configured to include a valve, a pressure adjustment bubble, and the like. Note that the pressure adjustment section 8 may be provided as necessary, or may be omitted.

Note that a cooler and a gas-liquid separator (not shown) may be provided in the middle of the gas line GL5 to cool the mixed gas.
The cooler generates condensed water (liquid) by cooling the mixed gas.
This cooler is a jacket-type cooling device in which a jacket is placed around the piping to allow the refrigerant to pass through, and has the same configuration as the first reactors 4a and 4b (see FIG. 2), and has a mixed gas inside the tube. , a multi-tubular cooling device that allows refrigerant to pass around each tube body, an air fin cooler, and the like.

The gas-liquid separator separates condensed water generated when the mixed gas is cooled by the cooler from the mixed gas. At this time, the condensed water has the advantage of being able to dissolve and remove unnecessary gas components (especially carbon dioxide) remaining in the mixed gas.
The gas-liquid separator can be constituted by, for example, a simple container, a swirling flow separator, a centrifugal separator, a surface tension separator, or the like. Among these, the gas-liquid separator is preferably constructed from a simple container because it is simple and inexpensive. In this case, a filter may be placed at the gas-liquid interface within the container to allow gas to pass through but to block liquid from passing through.

As described above, by removing water and unnecessary gas components from the mixed gas, a mixed gas with a higher concentration of carbon monoxide can be supplied to the third reactor 6. Therefore, it is possible to prevent or suppress a decrease in the conversion efficiency of carbon monoxide into a carbon material, and to further increase the amount of carbon monoxide produced.

The third reaction temperature in the third reactor (third reaction section) 6 is preferably lower than the first reaction temperature in the first reactors 4a, 4b (first reaction section 4). In this case, the reaction heat in the first reactors 4a, 4b can be effectively used in the third reactor 6.
Specifically, the third reaction temperature is preferably 850°C or lower, more preferably 800°C or lower, and even more preferably 750°C or lower. Thereby, it is possible to improve the production efficiency of carbon material and also increase the heat utilization efficiency. Note that the lower limit of the third reaction temperature is usually 600°C or higher.

A gas line GL7 is connected to the outlet port of the third reactor 6.
A second recovery section 9 is connected to the end of the gas line GL7 opposite the third reactor 6.
The second recovery unit 9 recovers carbon material from the gas generated in the third reactor 6 (product gas). This second recovery section 9 can be configured by combining one or more of an elutriation device, a centrifugal separator, an electrostatic precipitator, and a filter device, for example.
The second recovery unit 9 is connected to the gas line GL1 via the return gas line GL8. As described above, in the third reactor 6, a product gas containing not only carbon material but also carbon dioxide is produced from carbon monoxide.
Therefore, by passing through the second recovery section 9, the generated gas is separated into a carbon material and a generated gas containing carbon dioxide.

The generated gas after the carbon material has been recovered in the second recovery section 9 is returned to the first reactors 4a, 4b via the return gas line GL8 and the gas line GL1.
According to this configuration, the generated gas after passing through the second recovery section 9 can be effectively used without being discarded. As a result, it is possible to reduce carbon dioxide emissions and realize a circular economy (material recycling society). In particular, the generated gas after passing through the second recovery section 9 has a sufficiently high concentration of carbon dioxide, so even if it is mixed with the exhaust gas, the generated gas does not contain carbon dioxide or carbon monoxide in the first reactors 4a and 4b. It is possible to suitably prevent the conversion efficiency from decreasing.

Further, according to the above configuration, a carbon material with extremely low content of solid impurities is produced. Specifically, the content of solid impurities in the carbon material is preferably 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less. preferable. The lower limit of the content of solid impurities in the carbon material is not particularly limited, but is usually 0.001% by mass or more. Carbon materials with such a low content of solid impurities can prevent deterioration of their properties even when used in various electronic devices, various molded products, and the like.
Note that solid impurities include, for example, at least one of copper, zinc, iron, nickel, aluminum, chromium, and alloys containing these.

Such carbon materials can be used as reducing agents for smelting, secondary battery materials (e.g. negative electrode active materials, conductive aids for negative electrodes or positive electrodes), fillers for tires, and coloring agents for resin materials or rubber materials. , UV protection/absorbing material, fuel cell electrode material, and heat dissipation agent.
For example, if a carbon material is supplied to the blast furnace 1 together with ore, the carbon material functions as a reducing agent for smelting, and the target metal can be manufactured (smelted). Therefore, highly pure metal can be reliably obtained.
Further, for example, if a carbon material is used as a negative electrode active material of an ion secondary battery, it is possible to prevent short circuits from occurring in the ion secondary battery, deterioration of charge/discharge characteristics, etc. in the ion secondary battery.
Furthermore, for example, if a carbon material is used as a filler for a tire, it is possible to more appropriately suppress the deterioration of the elasticity and flexibility of the tire over time.

Next, a method of using the manufacturing system 10 (a method of manufacturing carbon valuables and carbon materials) will be described.
[1] First, by switching the gas line (flow path) in the gas switching unit 3, the blast furnace 1 and the first reactor 4a are connected, and the reducing gas supply unit 2 and the first reactor 4b are connected. do.
[2] Next, in this state, exhaust gas is supplied from the blast furnace 1 to the first reactor 4a via the gas line GL1. In the first reactor 4a, the reducing agent 4R reduces carbon dioxide and converts it into carbon monoxide by contacting with exhaust gas (source gas containing carbon dioxide). At this time, the reducing agent 4R is brought into an oxidized state by contact with carbon dioxide.

The temperature (first reaction temperature) of the first reactor 4a (exhaust gas, reducing agent 4R) in the above step [2] is preferably 500°C or higher, more preferably 650°C or higher and 1100°C or lower. The temperature is preferably 700°C or more and 1000°C or less.
Further, the pressure (first reaction pressure) of the first reactor 4a (exhaust gas, reducing agent 4R) is preferably less than 1 MPaG, more preferably 0.9 MPaG or less, and 0.2 MPaG or more. More preferably, it is .8 MPaG or less.
If the reaction conditions are set within the above range, for example, it is possible to prevent or suppress a rapid temperature drop in the reducing agent 4R due to an endothermic reaction when converting carbon dioxide to carbon monoxide. The reduction reaction of carbon dioxide can proceed more smoothly.

[3] In parallel with the above steps [1] and [2], water (reducing gas raw material) is supplied from the tank to the hydrogen generator (reducing gas supply unit 2) to generate hydrogen from water.
[4] Next, a reducing gas containing hydrogen is supplied from the hydrogen generator to the first reactor 4b via the gas line GL2. In the first reactor 4b, the reducing agent 4R in an oxidized state is reduced (regenerated) by contact with reducing gas (hydrogen). At this time, water is produced. In this case, hydrogen may be produced on-site, or may be purified elsewhere and then supplied from a pipeline or cylinder. As long as the hydrogen is green, there is no need to worry about the production method. Moreover, green hydrogen may be used for only a part of the hydrogen.

The temperature (reaction temperature) of the first reactor 4b (reducing gas, reducing agent 4R) in the above step [4] is preferably 500°C or higher, more preferably 650°C or higher and 1100°C or lower, More preferably, the temperature is 700°C or more and 1000°C or less.
Further, the pressure (first reaction pressure) of the first reactor 4b (reducing gas, reducing agent 4R) is preferably less than 1 MPaG, more preferably 0.9 MPaG or less, and 0.2 MPaG or more. More preferably, it is 0.8 MPaG or less.
If the reaction conditions are set within the above range, for example, it is possible to prevent or suppress a rapid temperature drop of the reducing agent 4R due to an endothermic reaction when reducing (regenerating) the reducing agent 4R in an oxidized state. The reduction reaction of the reducing agent 4R in the reactor 4b can proceed more smoothly.
In the embodiment, the above steps [2] to [4] constitute a first generation step of generating carbon monoxide from carbon dioxide.

[5] Next, the gases that have passed through the first reactors 4a and 4b are combined to generate a mixed gas. At this point, the temperature of the mixed gas is typically 200°C or more and 1000°C or less. If the temperature of the mixed gas at this point is within the above range, it means that the temperature inside the first reactors 4a, 4b is maintained at a sufficiently high temperature, and the carbon monoxide caused by the reducing agent 4R It can be determined that the conversion to 4R and the reduction of the reducing agent 4R by the reducing gas are progressing efficiently.

[6] Next, the mixed gas is passed through the gas component removing section 12 via the gas line GL4. At this time, gas components having a boiling point higher than the boiling point of CO are removed from the exhaust gas from the first reactors 4a, 4b.
In this embodiment, this step [6] constitutes a removal step for removing a gas component having a boiling point higher than the boiling point of CO from the exhaust gas generated in the first generation step.
[7] Next, the mixed gas that has passed through the gas component removal section 12 is supplied to the second reactor 5. In the second reactor 5 carbon monoxide is converted into carbon values.
In this embodiment, this step [7] constitutes a second generation step of generating carbon valuables from carbon monoxide.

[8] Next, the mixed gas that has passed through the second reactor 5 is passed through the first recovery section 7 via the gas line GL4. As a result, carbon valuables are recovered.
[9] Further, the mixed gas containing unreacted carbon monoxide discharged from the second reactor 5 is passed through the pressure adjustment section 8 via the gas line GL5. At this time, the pressure of the mixed gas increases.
In this embodiment, this step [9] constitutes a pressure adjustment step for increasing the pressure of the gas (mixed gas) generated in the second generation step.
[10] Next, the mixed gas that has passed through the pressure regulator 8 is supplied to the third reactor 6. In the third reactor 6 carbon monoxide is converted into carbon material.
In this embodiment, this step [10] constitutes a third generation step of generating a carbon material from unreacted carbon monoxide discharged from the second reactor 5.
The produced gas (mixed gas) containing the carbon material is then discharged to the second recovery section 9 via the gas line GL7.

[11] Next, in the second recovery section 9, the carbon material is separated and recovered from the generated gas containing the carbon material. As mentioned above, the content of solid impurities in the carbon material is preferably 1% by mass or less.
[12] Next, the generated gas after the carbon material has been recovered in the second recovery section 9 is returned to the first reactors 4a, 4b via the return gas line GL8 and the gas line GL1.
This exhaust gas passes through the above steps [1] to [10] to generate carbon material again.

<<Second embodiment>>
Next, a second embodiment of the manufacturing system of the present invention will be described.
FIG. 3 is a schematic diagram showing the configuration of a second embodiment of the manufacturing system of the present invention.
Hereinafter, the manufacturing system 10 of the second embodiment will be described, focusing on the differences from the manufacturing system 10 of the first embodiment, and omitting the description of similar matters.

In the second embodiment, gas lines GL6a and GL6b branch from the middle of gas lines GL4a and GL4b, and join together at gas merging portion J1 to form gas line GL6. Further, a switching valve is provided at the branch portion between the gas lines GL4a and GL4b and the gas lines GL6a and GL6b.
The exhaust gas discharged from the first reactors 4a, 4b passes through gas lines GL4a, GL4b, GL4 and is supplied to the second reactor 5. The reducing gas discharged from the first reactors 4a, 4b passes through the gas lines GL6a, GL6b, GL6, and is returned to the reducing gas supply unit 2 after, for example, water is removed.

That is, in this embodiment, the exhaust gas after passing through the first reactors 4a, 4b is separated from the reducing gas after passing through the first reactors 4a, 4b.
Then, the exhaust gas that has passed through the first reactors 4a, 4b is supplied to the second reactor 5 without merging with the reducing gas that has passed through the first reactors 4a, 4b.
According to this configuration, exhaust gas with reduced water contamination can be supplied to the second reactor 5. Therefore, it is possible to prevent or suppress a decrease in the conversion efficiency of carbon monoxide into a carbon material, and to further increase the amount of carbon monoxide produced.

<<Third embodiment>>
Next, a third embodiment of the manufacturing system of the present invention will be described.
FIG. 4 is a schematic diagram showing the configuration of a third embodiment of the manufacturing system of the present invention.
The manufacturing system 10 of the third embodiment will be described below, focusing on the differences from the manufacturing system 10 of the first embodiment, and will omit the description of similar matters.
The manufacturing system 10 of the third embodiment includes a separation section 11 that separates carbon dioxide from exhaust gas in the middle of the gas line GL1 (upstream of the first reaction section 4).

By passing through the separation section 11, the concentration of carbon dioxide in the exhaust gas can be increased. Thereby, the conversion efficiency of carbon dioxide into carbon monoxide in the first reactors 4a, 4b can be further improved.
Methods for separating carbon dioxide from exhaust gas include, for example, a low-temperature separation method (deep cooling method) separator, a pressure swing adsorption (PSA) method separator, a membrane separation method separator, and a temperature swing adsorption (TSA) method. separators, amine absorption type separators, amine adsorption type separators, etc., and one type of these can be used alone or two or more types can be used in combination.

In the first or second embodiment described above, in the first reactor 4a, 4b, when the exhaust gas comes into contact with the reducing agent 4R, carbon monoxide is generated by a reduction reaction of carbon dioxide, and oxygen released from carbon dioxide is generated. At least a portion of the element is captured by the reducing agent 4R, and then when the reducing gas contacts the reducing agent 4R, it is transferred to hydrogen (reducing substance) and water (an oxide of the reducing substance) is generated. That is, in the first reactors 4a and 4b, at least a portion of the oxygen element can be separated within the carbon dioxide reduction reaction system (reaction field).
The configuration shown in FIG. 5 can also be adopted as a reactor capable of separating at least a portion of the oxygen element within the carbon dioxide reduction reaction system.

<<Fourth embodiment>>
Next, a fourth embodiment of the manufacturing system of the present invention will be described.
FIG. 5 is a schematic diagram showing the configuration of the first reactor in the fourth embodiment.
The manufacturing system 10 of the fourth embodiment will be described below, focusing on the differences from the manufacturing system 10 of the first to third embodiments, and will omit descriptions of similar matters.

The first reaction section 4 shown in FIG. 5 is composed of a reactor (also called a reaction cell, an electrolytic cell, or an electrochemical cell) that electrochemically (using electrical energy) performs a reduction reaction of carbon dioxide.
The first reaction section 4 includes a housing 42, a cathode 45, an anode 46, and a solid electrolyte layer 47 provided within the housing 42, and a power source 48 electrically connected to the cathode 45 and anode 46. There is.
In this configuration, the space within the housing 42 is divided into left and right sections by a laminate of a cathode (reductant) 45, an anode 46, and a solid electrolyte layer 47.

The housing 42 includes a cathode inlet port 421a, a cathode outlet port 421b, an anode inlet port 422a, and an anode outlet port 422b. The cathode side inlet port 421a and the cathode side outlet port 421b communicate with the cathode chamber in the left side space in the housing 42, and the anode side inlet port 422a and the anode side outlet port 422b communicate with the anode chamber in the right side space in the housing 42. are doing.

The cathode 45 and the anode 46 each include a conductive carrier and a catalyst supported on the carrier.
The carrier can be made of a carbon material such as carbon fiber fabric (carbon cloth, carbon felt, etc.) or carbon paper.
Examples of catalysts include platinum group metals such as platinum, ruthenium, rhodium, palladium, osmium, and iridium, transition metals such as gold, alloys of these metals, and alloys of these metals with other metals. can be mentioned.

The solid electrolyte layer 47 can be composed of, for example, a fluorine-based polymer membrane having sulfonic acid groups (Nafion (registered trademark), etc.), a sulfo-based ion exchange resin membrane, or the like.
As the power source 48, it is preferable to use a power source that generates electricity as renewable energy. Thereby, the energy efficiency in producing generated gas containing carbon valuables can be further improved.

In the first reaction section 4, when exhaust gas (carbon dioxide and water) is supplied from the cathode side inlet port 421a, a reduction reaction of carbon dioxide and water occurs due to the action of the electrons supplied from the power supply 48 and the catalyst. Carbon monoxide and hydrogen are produced, as well as oxygen ions.
Carbon monoxide and hydrogen are discharged from the cathode side exit port 421b to the gas line (gas line GL4), and oxygen ions diffuse within the solid electrolyte layer 47 toward the anode 46. The oxygen ions that have reached the anode 46 are converted into oxygen by depriving them of electrons, and are discharged from the anode side exit port 422b.
In this configuration, carbon monoxide and hydrogen discharged from the cathode side outlet port 421b are supplied to the second reactor 5. In this case, a removal section for removing hydrogen may be provided in the middle of the gas line GL4.

Further, the manufacturing system 10 may be configured such that the first reaction section 4 performs the reaction expressed by the following equation 4, and the third reaction section 6 performs the following reaction expressed by the following equation 5.
Formula 4: CO ₂ + H ₂ → CO + H ₂ O
Formula 5: CO + H ₂ → C + H ₂ O
That is, it can be configured to perform the Bosch reaction through the first reaction section 4 and the third reaction section 6. Note that the reaction of Formula 4 and the reaction of Formula 5 may occur simultaneously.

In this case, the first reaction section 4 and the third reaction section 6 can use a reaction device (heat exchanger) similar to that described for the first reactors 4a and 4b, respectively, and a plate Type reactors, plate-fin reactors, spiral reactors, etc. can also be used.
Further, the usable catalyst preferably contains at least one metal element selected from Groups 2 to 15, and at least one metal element selected from Groups 5 to 10. It is more preferable to contain a species, and it is even more preferable to contain at least one of nickel, molybdenum, chromium, cobalt, tungsten, vanadium, ruthenium, iridium, iron, and the like.

The first reaction temperature in the first reaction section 4 is preferably 400°C or more and 1200°C or less, more preferably 500°C or more and 1000°C or less, and even more preferably 600°C or more and 800°C or less. The temperature is preferably 680°C or higher and 700°C or lower, particularly preferably.
The first reaction pressure in the first reaction section 4 is preferably 0.1 MPaG or more and 5 MPaG or less, more preferably 0.2 MPaG or more and 4.5 MPaG or less, and 0.25 MPaG or more and 4 MPaG or less. is more preferable, and particularly preferably 0.3 MPaG or more and 3.5 MPaG or less.

Further, the third reaction temperature in the third reaction section 6 is preferably 400°C or more and 1000°C or less, more preferably 450°C or more and 900°C or less, and 500°C or more and 800°C or less. is more preferable, and particularly preferably 550°C or more and 700°C or less.
The third reaction pressure in the third reaction section 6 is preferably 0.1 MPaG or more and 5 MPaG or less, more preferably 0.2 MPaG or more and 4.5 MPaG or less, and 0.25 MPaG or more and 4 MPaG or less. is more preferable, and particularly preferably 0.3 MPaG or more and 3.5 MPaG or less.

According to the manufacturing apparatus, manufacturing system, and manufacturing method as described above, after generating carbon valuables from carbon monoxide, the unreacted carbon monoxide is converted into carbon material, thereby improving the utilization efficiency of carbon monoxide. It is possible to improve the
In particular, the produced carbon material has a low content of solid impurities, so it can be used for various purposes.

Furthermore, it may be provided in each of the following embodiments.

(1) An apparatus for producing carbon valuables and carbon materials, including a first reaction section that generates carbon monoxide from carbon dioxide, and a second reaction section that generates the carbon valuables from the carbon monoxide. and a third reaction section that generates the carbon material from the unreacted carbon monoxide discharged from the second reaction section.

(2) In the manufacturing apparatus according to (1) above, the first reaction section is a reductant that converts the carbon dioxide into the carbon monoxide through a reduction reaction of the carbon dioxide generated by contact with the carbon dioxide-containing raw material gas. and at least one reactor capable of separating at least a portion of the oxygen element released from the carbon dioxide within the reduction reaction system.

(3) In the manufacturing apparatus according to (2) above, the reductant is a reducing agent that reduces the carbon dioxide and converts it into the carbon monoxide through contact with the raw material gas and is brought into an oxidized state. In the manufacturing apparatus, the reducing agent in an oxidized state is a reducing agent that is reduced by contact with a reducing gas containing a reducing substance.

(4) In the manufacturing apparatus according to (3) above, the first reaction section has a plurality of the reactors, and the raw material gas and the reducing gas are switched and supplied to each of the reactors. manufacturing equipment.

(5) The production apparatus according to (4) above, which is configured to separate the raw material gas after passing through the reactor and the reducing gas after passing through the reactor. .

(6) The manufacturing apparatus according to (5) above, wherein the raw material gas after passing through the reactor is supplied to the second reaction section.

(7) The manufacturing apparatus according to any one of (1) to (6) above, further comprising a recovery section that recovers the carbon material from the gas generated in the third reaction section. .

(8) In the manufacturing apparatus according to (7) above, the third reaction section generates carbon dioxide in addition to the carbon material from the carbon monoxide, and the recovery section and the first reaction section The manufacturing apparatus is configured to return the gas after recovering the carbon material in the recovery section to the first reaction section via a return gas line connecting to the first reaction section.

(9) In the manufacturing apparatus according to any one of (1) to (8) above, the carbon material may be a reducing agent for smelting, a secondary battery material, a filler for tires, a resin material, or A manufacturing device used for at least one of a coloring agent for rubber materials, a UV protection/absorbing material, a fuel cell electrode material, and a heat dissipating agent.

(10) A system for producing carbon valuables and carbon materials, comprising the production apparatus according to any one of (1) to (9) above, and a source gas containing carbon dioxide connected to the production apparatus. A manufacturing system comprising a gas supply section that supplies.

(11) The manufacturing system according to (10) above, further comprising a separation section that is provided between the gas supply section and the first reaction section and separates the carbon dioxide from the raw material gas. system.

(12) The manufacturing system according to (11) above, wherein the gas supply section is a furnace associated with a smelter.

(13) The manufacturing system according to (12) above, wherein the furnace associated with the smelter is a blast furnace.

(14) A method for producing carbon valuables and carbon materials, comprising a first generation step of generating carbon monoxide from carbon dioxide, and a second generation step of generating the carbon valuables from the carbon monoxide. and a third generation step of generating the carbon material from the unreacted carbon monoxide discharged from the second reaction section.
Of course, this is not the case.

As mentioned above, various embodiments according to the present invention have been described, but these are presented as examples and do not limit the scope of the invention in any way. The new embodiment can be implemented in various other forms, and various omissions, substitutions, and changes can be made without departing from the gist of the invention. The embodiment and its modifications are included within the scope and gist of the invention, and are included within the scope of the invention described in the claims and its equivalents.

For example, the manufacturing apparatus and manufacturing system of the present invention may each have any other additional configuration with respect to the above embodiment, or may be replaced with any configuration that exhibits a similar function. , some configurations may be omitted.
In addition, the manufacturing method of the present invention may include any other additional process with respect to the above embodiment, and may be replaced with any process that exhibits a similar function, and some The process may be omitted.
In the above embodiment, a gas containing hydrogen is representatively explained as the reducing gas, but the reducing gas may include hydrocarbons (for example, methane, ethane, acetylene, etc.) instead of or in addition to hydrogen. It is also possible to use a gas containing at least one selected from ammonia and ammonia.

Further, the first reactor in the present invention may be a reactor configured such that at least a part of the oxygen element released from carbon dioxide by the reduction reaction is not separated within the reduction reaction system.
Such a reactor is a reverse water gas shift reaction in which carbon dioxide and hydrogen are brought into contact with a reducing agent 4R at the same time to convert carbon dioxide into carbon monoxide and hydrogen (reducing substance) into water. Examples include devices that utilize
In this reactor, at least a portion of the oxygen element released from carbon dioxide is not separated from the reduction reaction system (reaction field) and reacts with hydrogen to produce water.
However, if a reactor is used that can separate at least a portion of the oxygen element released from carbon dioxide within the reduction reaction system (reaction field) as described above, the reaction products carbon monoxide and water can be separated. Since it becomes difficult for these to coexist in the system, it is possible to prevent or suppress a decrease in the conversion efficiency of carbon dioxide to carbon monoxide due to restrictions on chemical equilibrium.

Further, any configurations of the first to fourth embodiments described above may be combined.
For example, the first reaction section 4 can be configured with an electrochemical cell as shown in FIG. 5, and the third reaction section 6 can be configured with a reactor that performs the reaction of formula 5 above.

10: Manufacturing system 100: Manufacturing apparatus 1: Blast furnace 2: Reducing gas supply section 3: Gas switching section 4: First reaction section 4a: First reactor 4b: First reactor 41: Pipe body 42: Housing 421a: Cathode side inlet port 421b: Cathode side outlet port 422a: Anode side inlet port 422b: Anode side outlet port 43: Internal space 45: Cathode 46: Anode 47: Solid electrolyte layer 48: Power source 4R: Reducing agent 5: Second reactor (second reaction section)
6: Third reactor (third reaction section)
7: First recovery section 8: Pressure adjustment section 9: Second recovery section 11: Separation section 12: Gas component removal section GL1: Gas line GL2: Gas line GL3a: Gas line GL3b: Gas line GL4: Gas line GL4a : Gas line GL4b : Gas line GL5 : Gas line GL6 : Gas line GL6a : Gas line GL6b : Gas line GL7 : Gas line GL8 : Return gas line J : Gas merging section J1 : Gas merging section

Claims

An apparatus for producing carbon valuables and carbon materials,
a first reaction section that generates carbon monoxide from carbon dioxide;
a second reaction section that generates the carbon valuables from the carbon monoxide;
and a third reaction section that generates the carbon material from the unreacted carbon monoxide discharged from the second reaction section.
The manufacturing apparatus according to claim 1,
The first reaction section accommodates a reductant that converts the carbon dioxide into carbon monoxide through a reduction reaction of the carbon dioxide caused by contact with the carbon dioxide-containing raw material gas, and also stores the oxygen element released from the carbon dioxide. A manufacturing apparatus comprising at least one reactor capable of separating at least a portion of the reduction reaction within the system.
The manufacturing apparatus according to claim 2,
The reductant is a reducing agent that reduces the carbon dioxide and converts it into the carbon monoxide through contact with the raw material gas and is brought into an oxidized state, and the reducing agent in the oxidized state is a reducing agent containing a reducing substance. A manufacturing device that is a reducing agent that is reduced by contact with a gas.
The manufacturing apparatus according to claim 3,
The first reaction section has a plurality of the reactors,
A manufacturing apparatus in which the raw material gas and the reducing gas are selectively supplied to each of the reactors.
The manufacturing apparatus according to claim 4,
A manufacturing apparatus configured to separate the raw material gas after passing through the reactor and the reducing gas after passing through the reactor.
The manufacturing apparatus according to claim 5,
In the manufacturing apparatus, the raw material gas after passing through the reactor is supplied to the second reaction section.
In the manufacturing apparatus according to any one of claims 1 to 6,
The manufacturing apparatus further includes a recovery section that recovers the carbon material from the gas generated in the third reaction section.
The manufacturing apparatus according to claim 7,
The third reaction section generates carbon dioxide in addition to the carbon material from the carbon monoxide,
The gas after recovering the carbon material in the recovery section is configured to be returned to the first reaction section via a return gas line that connects the recovery section and the first reaction section. ,Manufacturing equipment.
In the manufacturing apparatus according to any one of claims 1 to 8,
The carbon material is a reducing agent for smelting, a secondary battery material, a filler for tires, a coloring agent for resin materials or rubber materials, a UV protection/absorbing material, a fuel cell electrode material, and a heat dissipating agent. Manufacturing equipment used for at least one.
A system for producing carbon valuables and carbon materials,
The manufacturing apparatus according to any one of claims 1 to 9,
A manufacturing system, comprising: a gas supply unit connected to the manufacturing apparatus and supplying a raw material gas containing carbon dioxide.
The manufacturing system according to claim 10,
The manufacturing system further includes a separation section that is provided between the gas supply section and the first reaction section and separates the carbon dioxide from the raw material gas.
The manufacturing system according to claim 11,
The manufacturing system, wherein the gas supply is a furnace associated with a smelter.
The manufacturing system according to claim 12,
A manufacturing system, wherein the furnace associated with the smelter is a blast furnace.
A method for producing carbon valuables and carbon materials, the method comprising:
a first generation step of generating carbon monoxide from carbon dioxide;
a second generation step of generating the carbon valuables from the carbon monoxide;
a third generation step of generating the carbon material from the unreacted carbon monoxide discharged from the second reaction section.