JP6011014B2 - Carbon dioxide gas decomposition apparatus and decomposition method - Google Patents

Description

The present invention relates to an apparatus and method for efficiently decomposing carbon dioxide gas (CO ₂ gas) into solid carbon and oxygen gas (O ₂ gas).

Global warming due to an increase in CO ₂ gas has been widely taken up as an international problem, and reducing the amount of emissions has become a global issue. For this reason, technical development for separating and recovering CO ₂ gas from gas generated from various facilities has been carried out, but no effective proposal has been made as to how to use the recovered CO ₂ gas. is the current situation.

That is, so far, a technique for filling the collected CO ₂ gas into the ground, so-called CCS (Carbon Dioxide Capture and Storage), has been actively researched mainly in Europe, the United States, Japan and the like. However, this technology is not only difficult to obtain social consensus, especially in Japan, which is an earthquake country, from the viewpoint of safety after CO ₂ gas is buried in the ground. According to a trial calculation by the Research Organization (RITE), the value obtained by dividing the CO ₂ embeddable amount in the vicinity of Japan including the near sea by the emission amount, that is, the lifetime is only about 50 to 100 years. Therefore, at least in Japan, CCS is unlikely to be a fundamental solution for reducing CO ₂ gas emissions.

By the way, according to statistics, Japan's CO ₂ gas emissions are about 30% due to power generation and 10% due to steel production. Yes. Of these, at the power plant, the chemical energy of coal, oil, and natural gas is converted into electric energy by complete oxidation of these fossil fuels, so the carbon contained in the fossil fuel is oxidized and the amount of fossil fuel used is determined. CO ₂ gas is inevitably discharged.
However, such fossil fuel power generation is expected to gradually decrease in the long term due to the use of so-called soft energy such as solar power generation, wind power generation, tidal power generation, and the spread of biomass power generation and nuclear power generation. Is done.

On the other hand, in steel production at steelworks, CO ₂ gas is generated in various processes, but the largest source is the blast furnace process. The generation of CO ₂ gas in this blast furnace process results from the reduction of oxygen in the iron ore by reducing iron ore, which is iron oxide, with the reducing material carbon.

In the blast furnace process, hot air of 1000 ° C or higher is blown from the lower part of the blast furnace, the coke is burned, the heat necessary for the reduction or melting of iron ore is supplied, and the reducing gas (CO gas) is generated. Reduce iron ore to obtain hot metal. For this reason, CO ₂ gas is also generated in steel production.

The inventors have so far proposed a method of reducing CO ₂ gas to decompose it into solid carbon and O ₂ gas. For example, Non-Patent Document 1, is passed through a CO ₂ gas in the molten salt to which a voltage is applied, by reducing CO ₂ gas as described for decomposing techniques to solid carbon and O ₂ gas.

42nd Molten Salt Chemistry Conference Abstracts (2010) P15-16 Presentation No. 1A08

However, for example, in the case of decomposing CO ₂ gas generated in an ironworks, the processing amount is enormous, and the CO ₂ gas decomposition processing amount can be increased compared to the technique described in Non-Patent Document 1. is necessary. For this purpose, to improve the decomposition efficiency of the CO ₂ gas becomes a problem.
Therefore, an object of the present invention is to propose an apparatus and method for efficiently decomposing CO ₂ gas into solid carbon and O ₂ gas.

The inventors diligently studied ways to solve the above problems. As described below, in the technique described in Non-Patent Document 1, CO ₂ was passed through the CO ₂ gas in the molten salt to which a voltage is applied, the alkali metal or alkaline earth metal atoms generated by electrolysis The gas is reduced and decomposed into solid carbon and O ₂ gas. We, As a result of intensive studies of ways of improving the decomposition efficiency of the CO ₂ gas in this reaction, to increase the contact area between the CO ₂ gas and the molten salt, and a CO ₂ gas contact time with the molten salt It is found that the decomposition efficiency of CO ₂ gas is improved by increasing the length, and for that purpose, a source gas introduction pipe having a plurality of blowing holes for generating bubbles of the source gas containing CO ₂ gas is prepared, and the electrode is made into a bubble. It has been found that it is effective to supply the raw material gas into the molten salt through the raw material gas introduction pipe under the arrangement above the generation region of the above, and the present invention has been completed.

That is, the gist configuration of the present invention is as follows.
(1) A carbon dioxide gas decomposing apparatus that causes carbon dioxide gas contained in a raw material gas to pass through a molten salt to which a voltage is applied to decompose the carbon dioxide gas in the molten salt into solid carbon and oxygen gas, An electrolytic cell containing a molten salt, an anode electrode and a cathode electrode, a pair of electrodes for applying a voltage to the molten salt, and a source gas introduction pipe for introducing the source gas into the molten salt, A source gas introduction pipe having a plurality of blowing holes for generating bubbles of the source gas on the surface of the source gas introduction pipe, and the pair of electrodes are disposed above the bubble generation area, and the anode An apparatus for decomposing carbon dioxide gas, wherein the number of electrodes is larger than the number of the cathode electrodes .

(2) The carbon dioxide gas decomposition apparatus according to (1), wherein the blowing hole is disposed below the cathode electrode.

(3) The carbon dioxide gas decomposition apparatus according to (1) or (2), wherein the anode electrode and the cathode electrode are plate-shaped.

(4) the raw material gas is an exhaust gas from the reduction furnace, wherein (1) to the device for decomposing carbon dioxide gas according to any one of (3).

(5) The raw material gas is an exhaust gas from the oxidation furnace, wherein (1) to the device for decomposing carbon dioxide gas according to any one of (3).

(6) The carbon dioxide gas contained in the source gas is passed through a molten salt to which a voltage is applied by a pair of electrodes consisting of an anode electrode and a cathode electrode, and the carbon dioxide gas in the molten salt is solid carbon and oxygen Upon decomposed into gas, the passage into the molten salt of the carbon dioxide gas, have rows by generating a bubble of the raw material gas at the lower of the pair of electrodes, the number of the anode electrode of the cathode electrode A method for decomposing carbon dioxide gas characterized in that the number is larger than the number .

(7) The generation of the bubbles is a raw material gas introduction pipe for introducing the raw material gas into the molten salt, and a raw material having a plurality of blowing holes for generating the raw material gas bubbles on the surface of the raw material gas introduction pipe The method for decomposing carbon dioxide gas according to (6), which is performed using a gas introduction pipe.

(8) The method for decomposing carbon dioxide gas according to (6) or (7), wherein the generation of the bubbles is performed such that all of the generated bubbles pass between the pair of electrodes.

(9) The carbon dioxide gas decomposition method according to any one of (6) to (8), wherein exhaust gas from a reduction furnace is supplied as the source gas.

(10) The method for decomposing carbon dioxide gas according to any one of (6) to (8), wherein exhaust gas from an oxidation furnace is supplied as the source gas.
(11) The carbon dioxide gas decomposition apparatus according to any one of (1) to (5), wherein the anode electrode includes a solid electrolyte having a closed end including zirconia.
(12) The said carbon dioxide gas decomposition | disassembly method as described in any one of said (6)-(10) provided with the solid electrolyte of the one end closed tube containing a zirconia.

According to the CO ₂ gas decomposition apparatus of the present invention, the apparatus includes a source gas supply pipe having a plurality of blowing holes for generating bubbles of the source gas in the molten salt, and the pair of electrodes are arranged above the bubble generation region. Since the source gas is supplied into the molten salt, the contact area between the CO ₂ gas and the electrode is increased, and the CO ₂ gas contained in the source gas is efficiently decomposed into solid carbon and O ₂ gas. Can do.
In addition, according to the method for decomposing CO ₂ gas of the present invention, since the gas bubbles of the source gas are generated below the pair of electrodes and supplied into the molten salt, the contact area between the CO ₂ gas and the electrode increases. The CO ₂ gas contained in the source gas can be efficiently decomposed into solid carbon and O ₂ gas.

The CO ₂ gas is a diagram illustrating the decomposed principles and solid carbon and oxygen gas. It is a diagram illustrating an example of a device for decomposing the CO ₂ gas of the present invention.

(Principle of CO ₂ gas decomposition)
Before describing the present invention, the principle of allowing CO ₂ gas to pass through a molten salt to which voltage has been applied and decomposing it into solid carbon and O ₂ gas will be described. FIG. 1 is a diagram for explaining the principle of decomposing CO ₂ gas into solid carbon and oxygen gas used in the technique described in Non-Patent Document 1. The CO ₂ gas decomposition apparatus 100 in this figure includes an electrolytic cell 11 that contains a molten salt, and a pair of electrodes 12 including an anode electrode 12a and a tubular cathode electrode 12b.

The decomposition process of CO ₂ gas using this apparatus 100 is performed as follows. That is, first, a molten salt material is put into the electrolytic cell 11, and the molten salt material is heated to a molten salt by a heater (not shown). Next, CO ₂ gas is passed through the molten salt. Thereafter, by applying a predetermined voltage between the anode electrode 12a and the cathode electrode 12b, the CO ₂ gas passed through the molten salt is reduced and decomposed into solid carbon and O ₂ gas.

Here, the principle of the decomposition of CO ₂ gas will be described in detail by taking as an example the case of using a mixture of CaO and CaCl ₂ as the molten salt. First, when CaO and CaCl ₂ charged into the electrolytic cell 11 are heated to a liquidus temperature (for example, 780 ° C.), CaO and CaCl ₂ are melted to obtain a molten salt. Here, most of CaO which comprises molten salt turns into Ca ^<2+> and O ^{<2- >} .
CaO → Ca ²⁺ + O ²⁻ (1)
CaCl ₂ exists as a molecule, and also exists as Ca ²⁺ and Cl ⁻ .
Next, a voltage not less than the decomposition voltage of CaO and not more than the decomposition voltage of CaCl ₂ is applied between the anode electrode 12a made of a ZrO ₂ -based solid electrolyte and the tubular cathode electrode 12b made of a metal plate, for example, SUS304 or 316 stainless steel. Then, the Ca ²⁺ ions receive electrons at the cathode electrode 12b and become Ca atoms.
Ca ²⁺ + 2e ⁻ → Ca (2)

Alkali metals and alkaline earth metals are immediately oxidized in the air, and therefore exist as oxides. However, the Ca ²⁺ ions receive electrons by the electrolysis and exist as atoms in the molten salt. Since the generated Ca atoms have a very high reducing ability, solid carbon is generated as a result of reducing the CO ₂ gas that has passed through the molten salt.
2Ca + CO ₂ → C + 2CaO (3)

Here, CaO is generated as a by-product. Since a voltage equal to or higher than the decomposition voltage of CaO is applied between the anode electrode 12a and the cathode electrode 12b, the CaO is electrolyzed to form CaO. ²⁺ and O ²⁻ . Thus, in the cathode electrode 12b, Ca atoms generated by electrolysis reduce CO ₂ gas to produce solid carbon.

On the other hand, in the anode electrode 12a, electrons are removed from the O ²⁻ ions to generate oxygen gas.
2O ²⁻ → O ₂ + 4e ⁻ (4)

By the above reaction, the CO ₂ gas introduced into the molten salt is reduced, O ₂ gas is generated at the anode electrode 12a, and solid carbon is generated at the cathode electrode 12b. The CO ₂ gas decomposition apparatus and decomposition method of the present invention also utilize the above-described principle and improve the efficiency of the decomposition reaction. Embodiments of the present invention will be described below with reference to the drawings.

(CO ₂ gas decomposition equipment)
First, the CO ₂ gas decomposition apparatus of the present invention will be described. FIG. 2 is a diagram showing an example of the CO ₂ gas decomposition apparatus of the present invention. Decomposing apparatus of the CO ₂ gas 1, the CO ₂ gas contained in the raw material gas, is passed through a molten salt of applying a voltage degrades the CO ₂ gas in the molten salt to solid carbon and O ₂ gas CO ₂ A gas decomposing apparatus comprising an electrolytic cell 21 containing molten salt, an anode electrode 22a and a cathode electrode 22b, a pair of electrodes 22 for applying a voltage to the molten salt, and introducing a raw material gas into the molten salt. The raw material gas introduction pipe 23 is provided with a raw material gas introduction pipe 23 having a plurality of blowing holes 23 a that generate bubbles of the raw material gas on the surface of the raw material gas introduction pipe 23. Here, it is important that the pair of electrodes 22 is disposed above the bubble generation region. In the apparatus 1 shown in FIG. 2, although it has the structure which has four pairs of electrodes 22 with respect to one electrolytic cell 21, it is not limited to this.

As described above, the inventors say that the decomposition efficiency of CO ₂ gas is improved by increasing the contact area between the CO ₂ gas and the molten salt and increasing the contact time between the CO ₂ gas and the molten salt. Under knowledge, a raw material gas supply pipe having a plurality of blowing holes for generating raw material gas bubbles in the molten salt is prepared, and the raw material gas is melted under a pair of electrodes arranged above the bubble generation region. It has been found that supplying inside is effective. The following describes each component of the decomposition apparatus of the CO ₂ gas of the present invention.

  The electrolytic cell 21 is a container for containing a molten salt, and a refractory mainly composed of magnesia or alumina can be used as the electrolytic cell 21. It is preferable to use dense magnesia because of its high durability.

  The pair of electrodes 22 includes an anode electrode 22a and a cathode electrode 22b. By applying a voltage between these electrodes, a voltage is applied to the molten salt accommodated in the electrolytic cell 21 to cause electrolysis.

Here, the anode electrode 22a is made of a solid electrolyte and an electric conductor such as a metal rod or graphite powder present therein, and the solid electrolyte includes rare earth oxides such as zirconia, calcium oxide, magnesium oxide, or yttrium oxide. To which stabilized zirconia or partially stabilized zirconia excellent in mechanical properties such as strength and toughness can be used. Among these, it is particularly preferable to use yttria-stabilized zirconia (ZrO ₂ —Y ₂ O ₃ ) excellent in ion conductivity.

  Moreover, in order to use as a material of the cathode electrode 22b, it is necessary to have high conductivity and to withstand the corrosion of the molten salt, and stainless steel, Inconel, or the like can be used. From the point of corrosivity, it is preferable to use SUS316 stainless steel.

Further, the shapes of the anode electrode 22a and the cathode electrode 22b are not particularly limited. However, since the contact area with the bubbles of the source gas can be increased and the decomposition efficiency of the CO ₂ gas can be improved, it may be a plate shape. preferable.

The raw material gas introduction pipe 23 is a pipe for supplying a raw material gas containing CO ₂ gas into the molten salt. As shown in FIG. 2, the surface has a plurality of blowing holes 23a for generating bubbles of the raw material gas. ing. In the conventional CO ₂ gas decomposition apparatus shown in FIG. 1, the cathode electrode 12b also functions as a source gas introduction pipe, and the source gas is introduced into the molten salt from the lower end of the cathode electrode 12b. Supplied. On the other hand, in the CO ₂ gas decomposition apparatus 1 of the present invention, when the raw material gas is introduced into the raw material gas introduction pipe 23, the raw material gas is supplied into the molten salt as bubbles smaller than before by the blowing holes 23a. Is done. Thus, increasing the contact area between the CO ₂ gas and the molten salt, the decomposition efficiency of the CO ₂ gas contained in the raw material gas is improved.

Here, since the introduction pipe 23 is provided with a plurality of blowing holes 23a, a large number of CO ₂ gases can be supplied into the electrolytic cell 21 by a small number of introduction pipes 23, and per introduction pipe. The amount of decomposition of CO ₂ can be increased. In addition, if a large amount of CO ₂ gas is supplied from one place, the agitation of the blowing portion becomes large and Ca generated in the vicinity of the anode electrode 22a may be dispersed, which may inhibit the decomposition reaction of the CO ₂ gas. The stirring can be suppressed by adjusting the number or density of the holes 23a to disperse the generation of bubbles at a plurality of locations.

Further, regarding the number of anode electrodes 22a and cathode electrodes 22b, the decomposition reaction of CO ₂ gas is rate-determined by the generation of oxygen gas at the anode electrode 22a. Therefore, by relatively increasing the number of anode electrodes 22a, The decomposition efficiency of CO ₂ gas can be increased.

In addition, it is important that the bubble generation region, that is, the blowing hole 23a is disposed below the pair of electrodes 22 (that is, the pair of electrodes 22 is disposed above the bubble generation region). Since the decomposition of the CO ₂ gas is performed while the raw material gas (that is, the CO ₂ gas) floats and passes through the molten salt, by disposing the bubble generation area below the pair of electrodes 22, The contact time between the CO ₂ gas supplied as small bubbles and the molten salt becomes longer, and the decomposition efficiency of the CO ₂ gas can be improved. As described above, in the CO ₂ gas decomposition apparatus 1 according to the present invention, the raw material gas is supplied to the molten salt as bubbles smaller than the conventional through the blow holes 23, and the bubble generation area is disposed below the pair of electrodes. Thus, by increasing the contact time between the CO ₂ gas and the molten salt, the decomposition efficiency of the CO ₂ gas is improved.

Further, the bubble generation area, that is, the horizontal position of the blowing hole 23a is below the cathode electrode where a large amount of Ca is present in the molten salt because the decomposition of the CO ₂ gas occurs by the reaction of the formula (3). It is preferable to arrange. Thus, it is possible to perform the decomposition of CO ₂ gas more efficiently.

  As a material for the source gas introduction pipe, it is necessary to have high conductivity and to withstand corrosion of molten salt, and stainless steel, Inconel, or the like can be used. SUS316 stainless steel is preferably used from the viewpoints of heat resistance, corrosivity, and economy.

Further, it is possible to control the diameter of the bubbles CO ₂ gas by adjusting the diameter of the blowing hole. For example, by reducing the bubbles of CO ₂ gas, the specific surface area is increased, and the reaction of formula (3) occurs on the surface of the bubbles, so that the throughput per unit volume of CO ₂ gas can be increased. The specific diameter of the blow hole 23a is appropriately set according to the number or density of the blow holes 23a and the gas introduction speed.

Thus, the CO ₂ gas decomposition apparatus of the present invention includes a raw material gas introduction pipe having a plurality of blowing holes for generating bubbles of the raw material gas, and the pair of electrodes are disposed above the bubble generation region. The contact area between the molten salt and the molten salt can be increased, and the CO ₂ gas contained in the raw material gas can be efficiently decomposed into solid carbon and O ₂ gas.

(CO ₂ gas decomposition method)
Next, the method for decomposing CO ₂ gas of the present invention will be described. The method for decomposing a CO ₂ gas of the present invention, the CO ₂ gas contained in the raw material gas, a voltage by a pair of electrodes composed of an anode electrode and a cathode electrode is passed through a molten salt applied in the molten salt Decompose CO ₂ gas into solid carbon and O ₂ gas. At that time, it is important to pass the CO ₂ gas into the molten salt by generating bubbles of the source gas below the pair of electrodes. Hereinafter, each step will be described with reference to FIG.

  First, a molten salt material is put into the electrolytic cell 21, and the molten salt material is heated by a heater (not shown) to form a molten salt. As the material of the molten salt, a mixture of metal chloride and metal oxide is used. Here, the metal chloride is one or more of alkali metal chloride and alkaline earth metal chloride, and the metal oxide is one of alkali metal oxide and alkaline earth metal oxide. Use a mixture with more than seeds.

As the alkali metal chloride, LiCl, NaCl, KCl or the like can be used, and as the alkaline earth metal chloride, MgCl ₂ , CaCl ₂ or the like can be used.
As the alkali metal _{oxides, Li 2 O, Na 2 O} , the _{K 2} O, etc., as the alkaline earth metal oxides may be used MgO, CaO, or the like, respectively.

  In addition, the molten salt needs to contain a metal oxide, but the ratio of the metal oxide contained in the molten salt is saturated from the point of decomposition efficiency in the solubility of the metal oxide in the metal chloride at the time of melting. It is preferable that the ratio be such.

Next, the source gas containing CO ₂ gas is introduced into the molten salt through the source gas introduction pipe 23 and allowed to pass therethrough. Here, it is important to pass the CO ₂ gas into the molten salt by generating bubbles of the raw material gas below the pair of electrodes 22. Specifically, this is a raw material gas introduction pipe for introducing a raw material gas containing CO ₂ gas into a molten salt, and a raw material gas introduction having a plurality of blowing holes 23a for generating bubbles of the raw material gas on the surface. This can be done by preparing the tube 23 and supplying the raw material gas into the molten salt with the pair of electrodes 22 arranged above the bubble generation region. When the raw material gas is introduced into the raw material gas introduction pipe 23, the raw material gas is supplied into the molten salt as bubbles having a smaller diameter than the conventional through the blow hole 23a, and the contact area between the CO ₂ gas and the molten salt increases and decomposes. Efficiency is improved.

Here, the source gas is not particularly limited as long as it contains at least CO ₂ gas. For example, when the present invention is carried out at a steel mill, exhaust gas discharged from a reduction furnace, an oxidation furnace, a combustion furnace or the like can be used, and the type thereof is not limited. For example, blast furnace gas and converter gas can be cited as typical examples, but the present invention is not limited thereto, and coke oven gas, heating furnace combustion exhaust gas, and the like can also be used. Among these, it is preferable to use blast furnace gas because the effect of reducing CO ₂ gas is high and the amount of solid carbon and oxygen gas obtained after decomposition is large.

Further, the concentration of the CO ₂ gas contained in the raw material gas is preferably high from the viewpoint of efficiently decomposing the CO ₂ gas when the raw material gas is introduced into the molten salt as it is. When blast furnace gas, converter gas, or heating furnace combustion exhaust gas is used as a raw material gas, the reaction frequency between metal atoms such as Ca and Li and CO ₂ is improved and decomposition can be efficiently performed, so that 15% by volume or more It is preferable that

Furthermore, when the introduction rate of the raw material gas into the molten salt is low, the decomposition efficiency of the CO ₂ gas is lowered. On the other hand, when the introduction speed is too high, convection of the molten salt occurs, and metal atoms such as Ca and Li generated in the vicinity of the electrode are dispersed. Therefore, it is appropriate considering the diameter and density of the blowing holes 23a. Set to value.

Thereafter, by applying a predetermined voltage between the anode electrode 22a and the cathode electrode 22b, the CO ₂ gas passed through the molten salt is decomposed to generate solid carbon and O ₂ gas. The voltage applied between the electrodes (that is, the molten salt) is not less than the decomposition voltage of the metal oxide. For example, when LiCl—Li ₂ O is used as the molten salt material, the theoretical decomposition voltage of Li ₂ O, which is a metal oxide, is 2.47 V, so the applied voltage is 2.47 V or higher. This is because if the metal oxide decomposition voltage is lower than the metal oxide, no metal atom as a reducing material is generated, so that the CO ₂ gas is not decomposed.

Here, the applied voltage is preferably not more than the decomposition voltage of the metal chloride. For example, when LiCl—Li ₂ O is used as the material for the molten salt, the theoretical decomposition voltage of LiCl, which is a chloride, is 3.46V, so that it is preferably 3.46V or less. When the applied voltage exceeds the decomposition voltage of metal chloride, chlorine gas is generated in addition to oxygen gas at the anode. Therefore, by setting the applied voltage to be equal to or lower than the decomposition voltage of chloride, the generation of chlorine gas is suppressed and only oxygen gas is generated. Therefore, it is convenient to reuse the oxygen gas in various applications such as steelworks. Not only is it good, but generation of chlorine gas can prevent high temperature corrosion of the device material and reduction of molten salt material in the electrolytic cell.

In addition, the higher the applied voltage, the greater the amount of electricity applied and the amount of reducing agent produced, which increases the amount of decomposition of CO ₂ , so it is high in the range from the decomposition voltage of the metal oxide to the decomposition voltage of the metal chloride. More preferably, the value is set.

As described above, according to the method for decomposing CO ₂ gas of the present invention, since the gas bubbles of the source gas are generated below the pair of electrodes and supplied to the molten salt, the contact area between the CO ₂ gas and the electrode is reduced. The CO ₂ gas contained in the raw material gas can be efficiently decomposed into solid carbon and O ₂ gas.

In the method for decomposing CO ₂ gas or the present invention, the raw material gas (e.g., reducing furnace, an oxidation furnace, and the exhaust gases discharged from the combustion furnace) in order to increase the concentration of CO ₂ gas contained in, CO ₂ gas Before the decomposition step, a step of separating and recovering CO ₂ gas from the raw material gas may be provided. As a result, the concentration of the CO ₂ gas that passes through or contacts the molten salt can be increased, and the decomposition rate of the CO ₂ gas can be increased.

The method for separating and recovering the CO ₂ gas from the raw material gas is not particularly limited. For example, the CO ₂ gas is liquefied or solidified by pressurization or cooling, the CO ₂ gas is absorbed in a basic aqueous solution such as caustic soda or amine. After that, a method of separating and recovering by heating or decompression, a method of separating and recovering CO ₂ gas components by adsorbing an adsorbent such as activated carbon or zeolite, a method of separating and recovering by heating or decompression, a method of separating and recovering by a CO ₂ separation membrane, etc. can do.

In the CO ₂ gas decomposition method of the present invention, the solid carbon produced in the cathode electrode 22b by the decomposition of the CO ₂ gas can be reused as a resource. For example, in a steelworks, it can be used as a reducing agent or auxiliary reducing agent in a blast furnace, a heat source or a carburizing material in a converter or the like.

On the other hand, O ₂ gas is generated at the anode electrode 22a, and this O ₂ gas can be recovered and used as, for example, an auxiliary combustion gas or an oxidant for blast furnaces, converters, heating furnaces, etc. .

Examples of the present invention will be described below.
First, CaCl ₂ —CaO, which is a molten salt material, was put into an electrolytic cell and heated with a heater to obtain a molten salt. Then, the raw material gas (90 _vol% CO 2 -10 vol% Ar) was passed through the molten salt at 100ml / min. Thereafter, a voltage was applied between the electrodes to decompose the CO ₂ gas into solid carbon and O ₂ gas. At that time, the number of anode electrodes made of a metal rod and a solid electrolyte, the number of cathode electrodes, the position of the cathode electrodes, and the CO ₂ gas blowing method were changed in various ways, and the amount of CO ₂ gas decomposed was investigated. Here, as the solid electrolyte constituting the anode electrode, a ZrO ₂ —Y ₂ O ₃ one-end closed tube was used, and the space between the metal rod and the solid electrolyte was filled with graphite powder. The temperature of the molten salt at the time of electrolysis is 900 ° C., and the voltage applied between the electrodes is 1.60 V or more which is the decomposition voltage of CaO which is a metal oxide, and the decomposition voltage of CaCl ₂ which is a chloride. It was set to 3.2V which is the range below 3.21V.
Further, the positions of the raw material gas blowing holes 23 were arranged so that all of the bubbles of the raw material gas to be formed passed between the electrodes in the inventive examples 1 to 6. The obtained results are shown in Table 1. Here, the CO ₂ gas throughput ratio is meant the amount of processing in the case of a 1 CO ₂ gas throughput of Comparative Example 1. The CO ₂ gas treatment amount is specifically the concentration of CO ₂ gas contained in the raw material gas before being introduced into the molten salt, was calculated from the concentration of CO ₂ gas after passing through the molten salt.

Under all conditions, solid carbon was generated from the molten salt and could be recovered. Further, oxygen gas was generated from the inside of the anode electrode and could be recovered.
In Comparative Example 1, as shown in FIG. 1, also serves as a one anode electrode and the CO ₂ gas blowing tube in the molten salt is performed under a condition of using the cathode electrode of one tubular, CO ₂ process gas The amount was 6.2 ml / min.
In Invention Example 1, as shown in FIG. 2, carried out under the conditions used and four anode in the molten salt, and four dedicated cathode and a source gas inlet pipe having a plurality of blowing holes, CO ₂ The gas throughput was 82.4 ml / min, which was 13.3 times the throughput of Comparative Example 1.
In Invention Example 2, it is carried out under conditions using two anode electrodes, two dedicated cathode electrodes, and a raw material gas introduction pipe having a plurality of blowing holes in the molten salt, and the CO ₂ gas throughput is 51.5 ml. The amount of treatment was 8.3 times that of Comparative Example 1.
In Invention Example 3, the measurement was performed under the conditions using one anode electrode, two dedicated cathode electrodes, and a raw material gas introduction pipe having a plurality of blow holes in the molten salt, and the CO ₂ gas throughput was 45.8 ml. The amount of treatment was 7.4 times that of Comparative Example 1.
In Invention Example 4, it is carried out under conditions using two anode electrodes, one dedicated cathode electrode, and a raw material gas introduction pipe having a plurality of blowing holes in the molten salt, and the CO ₂ gas throughput is 48.1 ml. The amount of treatment was 7.8 times that of Comparative Example 1.
In Invention Example 5, it is carried out under the condition of using one anode electrode, one dedicated cathode electrode, and a raw material gas introduction pipe having a plurality of blowing holes in the molten salt, and the CO ₂ gas throughput is 28.6 ml. The amount of processing was 4.6 times that of Comparative Example 1.
In Invention Example 6, one anode electrode, one dedicated cathode electrode, and a raw material gas were blown from a single tube into the molten salt, and the CO ₂ gas throughput was 11.6 ml / min. Comparative Example 1 The amount of treatment was 1.9 times.
Thus, in the invention Examples 1-6, the processing amount of CO ₂ gas is increased relative to Comparative Example 1, it can be seen that the decomposition efficiency of the CO ₂ gas is improved.

The reducing gas generated from the blast furnace was used as a raw material gas and allowed to pass through the molten salt at 100 ml / min to decompose the CO ₂ gas. All other conditions are the same as in Example 1. The composition of the blast furnace gas used is shown in Table 2, and the obtained results are shown in Table 3.

Under all conditions, solid carbon was generated from the molten salt and could be recovered. Further, oxygen gas was generated from the inside of the anode electrode and could be recovered.
In Comparative Example 2, as shown in FIG. 1, the amount of CO ₂ gas was processed under the condition of using one anode electrode in a molten salt and one tubular cathode electrode that also served as a CO ₂ gas blowing tube. Was 1.4 ml / min.
As shown in the present invention 7 in FIG. 2, four anode in the molten salt, and four dedicated cathode, performed under the condition of using a raw material gas introduction pipe having a plurality of blowing holes, CO ₂ gas The processing amount was 18.1 ml / min, which was 12.9 times the processing amount as compared with Comparative Example 1.
In the present invention 8, and two anode in the molten salt, and two dedicated cathode, performed under the condition of using a raw material gas introduction pipe having a plurality of blowing holes, the processing amount of CO ₂ gas 11.4ml The amount of treatment was 8.1 times that of Comparative Example 2.
In the ninth aspect of the present invention, the molten salt is used under the condition that one anode electrode, two dedicated cathode electrodes, and a raw material gas introduction pipe having a plurality of blowing holes are used, and the CO ₂ gas throughput is 9.6 ml. The amount of treatment was 6.9 times that of Comparative Example 2.
In the present invention 10, the process is carried out under conditions using two anode electrodes, one dedicated cathode electrode, and a source gas introduction pipe having a plurality of blowing holes in the molten salt, and the CO ₂ gas throughput is 11.2 ml. The amount of treatment was 8.0 times that of Comparative Example 2.
In the present invention 11, carried out at the conditions used and one anode in the molten salt, and one dedicated cathode and a source gas inlet pipe having a plurality of blowing holes, the processing amount of CO ₂ gas 6.8ml The amount of treatment was 4.9 times that of Comparative Example 2.
In the present invention 12, one anode electrode, one dedicated cathode electrode, and a raw material gas are blown from a single tube into the molten salt, and the CO ₂ gas throughput is 2.4 ml / min. The amount of treatment was 1.7 times that of.

Part of the solid carbon obtained in Invention Examples 1 to 12 was replaced with a part or all of the coal in a coke oven to be coke, and used as a reducing agent in the blast furnace. In addition, a part of the remaining solid carbon was blown from the tuyere's tuyere as part of the pulverized coal and reused as an auxiliary reducing agent in the blast furnace. Furthermore, all the remaining solid carbon was briquetted and reused as a carburizing material as a substitute for earth graphite in the converter. All this could be done without problems.
As mentioned above, the operation of a blast furnace and a converter was able to be performed without a problem using the obtained solid carbon.

1,100 CO ₂ gas decomposition apparatus 11, 21 Electrolyzer 12, 22 Pair of electrodes 12a, 22a Anode electrode 12b, 22b Cathode electrode 23 Raw material gas introduction pipe 23a Blow hole

Claims (12)

A carbon dioxide gas decomposing apparatus that decomposes the carbon dioxide gas in the molten salt into solid carbon and oxygen gas by passing the carbon dioxide gas contained in the raw material gas through the molten salt to which a voltage is applied,
An electrolytic cell containing the molten salt;
A pair of electrodes consisting of an anode electrode and a cathode electrode for applying a voltage to the molten salt;
A raw material gas introduction pipe for introducing the raw material gas into the molten salt, the raw material gas introduction pipe having a plurality of blowing holes for generating bubbles of the raw material gas on the surface of the raw material gas introduction pipe;
The pair of electrodes is disposed above the bubble generation area ,
The carbon dioxide gas decomposition apparatus, wherein the number of the anode electrodes is larger than the number of the cathode electrodes .   The carbon dioxide gas decomposition apparatus according to claim 1, wherein the blowing hole is disposed below the cathode electrode.   The carbon dioxide gas decomposition apparatus according to claim 1, wherein the anode electrode and the cathode electrode are plate-shaped. The raw material gas is an exhaust gas from the reduction furnace, decomposition apparatus of carbon dioxide gas according to any one of claims 1 to 3. The raw material gas is an exhaust gas from the oxidation furnace, cracker carbon dioxide gas according to any one of claims 1 to 3. The carbon dioxide gas contained in the source gas is passed through a molten salt to which a voltage is applied by a pair of electrodes consisting of an anode electrode and a cathode electrode, and the carbon dioxide gas in the molten salt is decomposed into solid carbon and oxygen gas. In doing so,
Passing into the molten salt of the carbon dioxide gas, have rows by generating a bubble of the raw material gas at the lower of the pair of electrodes, the number of the anode electrode to be larger than the number of the cathode electrode A method for decomposing carbon dioxide gas characterized by the above.   The generation of the bubbles is a source gas introduction pipe for introducing the source gas into the molten salt, and a source gas introduction pipe having a plurality of blowing holes for generating bubbles of the source gas on the surface of the source gas introduction pipe The method for decomposing carbon dioxide gas according to claim 6 performed using   The method for decomposing carbon dioxide gas according to claim 6 or 7, wherein the generation of the bubbles is performed so that all of the generated bubbles pass between the pair of electrodes.   The method for decomposing carbon dioxide gas according to any one of claims 6 to 8, wherein exhaust gas from a reduction furnace is supplied as the source gas.   The method for decomposing carbon dioxide gas according to any one of claims 6 to 8, wherein exhaust gas from an oxidation furnace is supplied as the source gas. The said anode electrode is a carbon dioxide gas decomposition | disassembly apparatus as described in any one of Claims 1-5 provided with the solid electrolyte of the one end closed tube containing a zirconia. The said anode electrode is a decomposition method of the carbon dioxide gas as described in any one of Claims 6-10 provided with the solid electrolyte of the one end closed tube containing a zirconia.

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