Method for producing methanol and apparatus for producing methanol

Abstract

To provide a novel method for producing methanol that enables easy production of high-purity methanol from carbon dioxide.SOLUTION: A method for producing methanol comprises an oxidation step in which a first material containing an oxygen carrier is contacted with carbon dioxide and hydrogen to yield a second material containing an oxide of the oxygen carrier and methanol.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a method for producing methanol and a production apparatus therefor.

Background Art

[0002] Conventionally, as one means for carbon dioxide fixation, a method for producing methanol from carbon dioxide has been studied. For example, Patent Document 1 discloses a method for producing methanol by reacting a raw material gas containing hydrogen and carbon dioxide in the presence of methanol and a catalyst composed of an oxide containing copper and zinc.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, in the method of Patent Document 1, water is generated as a by-product, so a step of separating methanol and water is necessary to obtain high-purity methanol.

[0005] One object of the present disclosure is to provide a novel method for producing methanol capable of easily producing high-purity methanol from carbon dioxide, and a production apparatus capable of implementing the production method.

Means for Solving the Problems

[0006] The present disclosure relates to, for example, the following [1] to

[12] . [1] A method for producing methanol, comprising an oxidation step of bringing a first material containing an oxygen carrier into contact with carbon dioxide and hydrogen to obtain a second material containing an oxide of the oxygen carrier and methanol. [2] The second material is recycled as the first material after being subjected to a reduction treatment, the manufacturing method according to [1]. [3] The manufacturing method according to [1] or [2], further comprising a reduction step of bringing the second material into contact with hydrogen to reduce the oxide to obtain the first material and water. [4] The manufacturing method according to [4], wherein the oxidation step and the reduction step are alternately carried out. [5] It is carried out by a manufacturing apparatus including an oxidation treatment unit that carries out the oxidation step and a reduction treatment unit that carries out the reduction step, the second material generated in the oxidation step is supplied from the oxidation treatment unit to the reduction treatment unit, the first material generated in the reduction step is supplied from the reduction treatment unit to the oxidation treatment unit. The manufacturing method according to [3] or [4]. [6] The manufacturing method according to any one of [1] to [5], wherein the first material includes an active site for the hydrogenation reaction of carbon monoxide. [7] The manufacturing method according to any one of [1] to [6], wherein the first material includes an active site for the hydrogenation reaction of carbon dioxide. [8] The manufacturing method according to any one of [1] to [7], wherein the oxygen carrier includes cobalt and at least one selected from the group consisting of copper and indium. [9] The manufacturing method according to any one of [1] to [7], wherein the oxygen carrier includes indium and at least one selected from the group consisting of cobalt, copper, and nickel.

[10] The manufacturing method according to [8] or [9], wherein the first material includes a carrier and the oxygen carrier supported on the carrier.

[11] The manufacturing method according to any one of [1] to

[10] , wherein the reaction temperature in the oxidation step is 280°C or higher and 400°C or lower.

[12] An oxidation treatment unit that brings a first material containing an oxygen carrier into contact with carbon dioxide and hydrogen to produce a second material containing an oxide of the oxygen carrier and methanol; A reduction treatment unit that brings the second material into contact with hydrogen to reduce the oxide and produce the first material and water; First transfer means for transferring the second material from the oxidation treatment unit to the reduction treatment unit; Second transfer means for transferring the first material from the reduction treatment unit to the oxidation treatment unit; A manufacturing apparatus comprising:

Advantages of the Invention

[0007] According to the present disclosure, there are provided a novel method for producing methanol capable of easily producing high-purity methanol from carbon dioxide, and a manufacturing apparatus capable of implementing the production method.

Brief Description of the Drawings

[0008]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0009] Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the drawings. The embodiments are illustrative rather than limiting the technical scope of the present disclosure, and within the scope not departing from the inventive concept, design changes such as component modifications, additions, deletions, etc. are possible. Also, the components described as embodiments can be arbitrarily combined.

[0010] In each drawing, the same or equivalent components, members, processes, etc. are denoted by the same reference numerals, and redundant descriptions are omitted. Also, the scales and shapes of the respective parts shown in each drawing are set for convenience in order to facilitate the explanation, and are not to be construed restrictively unless otherwise specified. Further, members that are not important in explaining the embodiments may be omitted in each drawing.

[0011] The manufacturing method of the present embodiment includes an oxidation step of bringing a first material containing an oxygen carrier into contact with carbon dioxide and hydrogen to obtain a second material containing an oxide of the oxygen carrier and methanol.

[0012] In the manufacturing method of the present embodiment, methanol is produced by the reaction of an oxygen carrier (MO x-1 ) with carbon dioxide and hydrogen as follows. In this reaction, since the oxygen carrier captures oxygen atoms, water is less likely to be produced as a by-product. Therefore, according to the manufacturing method of the present embodiment, high-purity methanol can be efficiently obtained. 2H 2 +CO 2 +MO x-1 →CH 3 OH+MO x

[0013] The second material containing the oxide of the oxygen carrier may be reductively treated and reused as the first material. By the reductive treatment, the oxide of the oxygen carrier changes to the oxygen carrier. The reductive treatment may be carried out, for example, by bringing the second material into contact with hydrogen.

[0014] The manufacturing method of the present embodiment may further include a reduction step of bringing the second material into contact with hydrogen to obtain the first material and water. By carrying out the oxidation step and the reduction step as separate steps, mixing of the methanol produced in the oxidation step and the water produced in the reduction step can be avoided.

[0015] The manufacturing method of this embodiment may be one in which the oxidation step and the reduction step are performed alternately. By performing the oxidation step and the reduction step alternately, continuous methanol production is possible by repeated use of the oxygen carrier.

[0016] The manufacturing method of this embodiment may be performed by a manufacturing apparatus including an oxidation processing unit that performs the oxidation step and a reduction processing unit that performs the reduction step. In the manufacturing apparatus, the second material generated in the oxidation step may be supplied from the oxidation processing unit to the reduction processing unit, and the first material generated in the reduction step may be supplied from the reduction processing unit to the oxidation processing unit. The manufacturing apparatus may include an oxidation processing unit, a reduction processing unit, a first transfer means for transferring the second material from the oxidation processing unit to the reduction processing unit, and a second transfer means for transferring the first material from the reduction processing unit to the oxidation processing unit.

[0017] In the manufacturing method of this embodiment, carbon dioxide and hydrogen may be circulated through a reactor filled with a first material to carry out an oxidation step, and hydrogen may be circulated through the reactor after the oxidation step to carry out a reduction step.

[0018] The manufacturing method of this embodiment may be carried out using a chemical looping system. In this case, the oxygen carrier (or the first material) can be called a reduced form (MO x-y ) of a material for a chemical looping system, and the oxide (or the second material) of the oxygen carrier can be called an oxidized form (MO x ) of a material for a chemical looping system. The chemical looping system material changes from the reductant MO x-y to the oxidant MO x by oxidation, and from the oxidant MO x to the reductant MO x-y by reduction. x and y are real numbers greater than 0, and satisfy the relationship x>y. In the following, MO x-1 is used as an example of a reductant, but the reductant may be MO x-y such as MO x-2 where y is a number other than 1. Multiple types of reductants may be present.

[0019] Figure 1 is a schematic diagram showing an example of a chemical looping system. In the chemical looping system 1 shown in Figure 1, the oxidation treatment and the reduction treatment of the material for the chemical looping system as a mediator are alternately repeated. The chemical looping system 1 includes an oxidation treatment unit 2, a reduction treatment unit 4, and a circulation path 6 connecting the oxidation treatment unit 2 and the reduction treatment unit 4.

[0020] The oxidation treatment unit 2 is, for example, an oxidation tower, and a reductant of the material for the chemical looping system (MO in Figure 1) exists in the oxidation treatment unit 2. x-1 In addition, carbon dioxide (CO 2 ) and hydrogen (H 2 ) are supplied from the outside to the oxidation treatment unit 2.

[0021] For the carbon dioxide supplied to the oxidation treatment unit 2, the carbon dioxide contained in the exhaust gas or the like can be used. Thereby, it is possible to contribute to the realization of carbon neutrality. The source of carbon dioxide is not particularly limited. For the hydrogen supplied to the oxidation treatment unit 2, for example, hydrogen generated using renewable energy such as sunlight or wind power can be used. Thereby, the amount of carbon dioxide emissions associated with the operation of the chemical looping system 1 can be reduced, and it is possible to contribute to the realization of carbon neutrality. The source of hydrogen is not particularly limited.

[0022] The ratio of carbon dioxide and hydrogen supplied to the oxidation treatment unit 2 is not particularly limited. The molar ratio of hydrogen to carbon dioxide (H 2 / CO 2 ) supplied to the oxidation treatment unit 2 may be, for example, 1 to 10, or may be 2 to 3.

[0023] When the inside of the oxidation treatment unit 2 is heated to a predetermined oxidation treatment temperature, the reductant, carbon dioxide, and hydrogen react to form an oxidant (MO in Figure 1) xAnd methanol is produced. In the oxidation treatment unit 2, carbon monoxide, methane, etc. may be further produced. The oxidation treatment temperature is, for example, 280°C to 400°C. The produced methanol is taken out of the system together with unreacted carbon dioxide and hydrogen and used for any purpose.

[0024] The oxidized substance (MO x ) produced by the oxidation treatment in the oxidation treatment unit 2 is sent to the reduction treatment unit 4 via the circulation path 6.

[0025] The reduction treatment unit 4 is, for example, a reduction tower. Reducing agents such as hydrogen; hydrocarbons; oxygen-containing hydrocarbons such as alcohols and carboxylic acids; carbon monoxide; hydrazine; hydrogen sulfide; potassium iodide; hydrogen peroxide; and mixtures thereof are supplied to the reduction treatment unit 4 from the outside. FIG. 1 shows a case where hydrogen is used as an example of the reducing agent.

[0026] For the hydrogen supplied to the reduction treatment unit 4, for example, hydrogen produced using renewable energy such as sunlight or wind power can be used. Thereby, the amount of carbon dioxide emissions associated with the operation of the chemical looping system 1 can be reduced, and it can contribute to the realization of carbon neutrality. Note that the source of hydrogen is not particularly limited.

[0027] When the inside of the reduction treatment unit 4 is heated to a predetermined reduction treatment temperature, the oxidized substance (MO x ) reacts with hydrogen to produce a reduced substance (MO x-1 ) and water. The reduction treatment temperature is, for example, 280°C to 1000°C. This step corresponds to a reduction treatment (reduction process) of returning the oxidized substance (MO x ) to the reduced substance (MO x-1 ). The produced water is taken out of the system together with unreacted hydrogen. Note that a part of the oxidized substance (MO x ) can also be changed to the reduced substance (MO x-1 ) only by heating.

[0028] The reduced substance (MO x-1 ) produced in the reduction process is sent to the oxidation treatment unit 2 via the circulation path 6. This reduced substance (MOx-1 ) is used for the oxidation treatment and becomes an oxidized form (MO x ) again. Thereafter, the oxidation treatment and the reduction treatment of the material for the chemical looping system are alternately repeated, and methanol is continuously produced.

[0029] The heat required for the chemical looping system 1 can be obtained from clean energy such as solar heat. Thereby, it is possible to contribute to the realization of a carbon-neutral cycle. Note that the heat supply source is not particularly limited.

[0030] FIG. 1 shows a fluidized bed type chemical looping system 1 in which the material for the chemical looping system travels between the oxidation treatment section 2 and the reduction treatment section 4. However, the structure of the chemical looping system is not limited to the fluidized bed type, and may be, for example, a fixed bed type (switching method).

[0031] FIGS. 2(A) to 2(D) are schematic diagrams showing a fixed bed type chemical looping system, which is another example of the chemical looping system.

[0032] As shown in FIGS. 2(A) to 2(D), in the case of the fixed bed type, for one reactor 8 filled with the material for the chemical looping system, carbon dioxide (CO 2 ) and hydrogen (H 2 ) supply and the supply of a reducing agent (H in FIG. 2(A) 2 ) are alternately switched, and the oxidation treatment and the reduction treatment of the material for the chemical looping system are repeated. That is, one reactor 8 functions as an oxidation treatment section and a reduction treatment section. The material for the chemical looping system functions as an oxygen carrier that transports oxygen from the oxidation treatment section to the reduction treatment section or from carbon dioxide to the reducing agent during the repetition of the oxidation treatment and the reduction treatment.

[0033] As an operation example of the fixed bed type chemical looping system, first, as shown in FIG. 2(A), the oxidized form (MO of the material for the chemical looping system x) A reducing agent is supplied to the reactor 8 filled with x ). In Fig. 2(A), hydrogen is illustrated as the reducing agent. When the inside of the reactor 8 is heated to a predetermined reduction treatment temperature, the oxide (MO x-1 ) and hydrogen react to produce a reduced body (MO x ) and water (reduction step). The generated water is taken out of the system together with the unreacted hydrogen. Note that a part of the oxide (MO x-1 ) can be changed to a reduced body (MO

[0034] Next, as shown in Fig. 2(B), a known purge gas is supplied to the reactor 8 filled with the reduced body (MO x-1 ), and the atmosphere inside the reactor 8 is replaced with the purge gas. The purge gas may be, for example, argon, nitrogen, or the like.

[0035] Subsequently, as shown in Fig. 2(C), carbon dioxide (CO 2 ) and hydrogen (H 2 ) are supplied to the reactor 8. When the inside of the reactor 8 is heated to a predetermined oxidation treatment temperature, the reduced body (MO x-1 ) reacts with carbon dioxide and water to produce an oxide (MO x ) and methanol (CH 3 OH) (oxidation step). The generated methanol is taken out of the system together with the unreacted carbon dioxide and hydrogen and used for any purpose.

[0036] Thereafter, as shown in Fig. 2(D), a known purge gas is supplied to the reactor 8 filled with the oxide (MO x ), and the atmosphere inside the reactor 8 is replaced with the purge gas. The purge gas may be, for example, argon, nitrogen, or the like, and may be the same purge gas as that in Fig. 2(B). Thereafter, the steps shown in Figs. 2(A) to 2(D) are repeated, and methanol is continuously produced.

[0037] The first material may contain active sites for the hydrogenation reaction of carbon monoxide. When such a first material is used, carbon monoxide is generated from carbon dioxide by an oxygen carrier, and the generated carbon monoxide is converted to methanol at the active sites.

[0038] The first material may contain active sites for the hydrogenation reaction of carbon dioxide on the oxygen carrier. When such a first material is used, the carbon dioxide activated on the active sites of the oxygen carrier is hydrogenated to produce methanol.

[0039] The first material may be composed only of an oxygen carrier, or may include a carrier and an oxygen carrier supported on the carrier.

[0040] In the first material, the carrier may be, for example, an inorganic oxide carrier. Examples of the carrier include ceria (CeO 2 ), alumina (Al 2 O 3 ), magnesia (MgO), silica (SiO 2 ), titania (TiO 2 ), zirconia (ZrO 2 ) and composite oxides thereof, etc.

[0041] The oxygen carrier may contain two or more elements selected from the group consisting of, for example, indium (In), cobalt (Co), copper (Cu), nickel (Ni), iron (Fe), cerium (Ce), praseodymium (Pr), gallium (Ga), chromium (Cr) and manganese (Mn).

[0042] The oxygen carrier is oxidized from a reduced form (MO x-y ) to an oxidized form (MO x ), and reduced from the oxidized form (MO x ) to the reduced form (MO x-y) needs to be convertible. From the perspective of significantly obtaining such a function, the oxygen carrier preferably contains at least one first element selected from the group consisting of indium (In), cobalt (Co), copper (Cu), nickel (Ni), iron (Fe), cerium (Ce), praseodymium (Pr), gallium (Ga), chromium (Cr), and manganese (Mn). As the first element, indium (In), cobalt (Co), and copper (Cu) are preferred, and indium (In) is more preferred.

[0043] The oxygen carrier may contain an active site for the hydrogenation reaction of carbon monoxide. From the perspective of functioning as the active site, the oxygen carrier preferably contains at least one second element selected from the group consisting of cobalt (Co), copper (Cu), nickel (Ni), palladium (Pd), chromium (Cr), and manganese (Mn). As the second element, cobalt (Co), copper (Cu), and nickel (Ni) are preferred, and cobalt (Co) is more preferred.

[0044] The oxygen carrier may contain an active site that plays a role in promoting the Redox reaction as an active site for carbon dioxide. From the perspective of functioning as the active site, the oxygen carrier preferably contains at least one second element selected from the group consisting of cobalt (Co), copper (Cu), nickel (Ni), chromium (Cr), and manganese (Mn).

[0045] In a preferred embodiment, the oxygen carrier may contain cobalt (Co) and at least one selected from the group consisting of copper (Cu) and indium (In). Such an oxygen carrier contains cobalt, which is particularly suitable as an active site, and copper or indium, which greatly contributes to the oxygen transport ability, and thus has excellent methanol production efficiency.

[0046] In another suitable embodiment, the oxygen carrier may include indium (In) and at least one selected from the group consisting of cobalt (Co), copper (Cu), and nickel (Ni). Such an oxygen carrier contains cobalt, copper, or nickel, which is suitable as an active site, and indium, which contributes particularly greatly to the oxygen transport ability, and thus is excellent in the production efficiency of methanol.

[0047] In a more suitable embodiment, the oxygen carrier may include indium and cobalt. Such an oxygen carrier contains cobalt, which is particularly suitable as an active site, and indium, which contributes particularly greatly to the oxygen transport ability, and thus is even more excellent in the production efficiency of methanol.

[0048] When the first material contains a carrier and an oxygen carrier, the content of the oxygen carrier may be, for example, 5 to 40 mol% based on the total amount of the first material, or may be 10 to 15 mol%.

[0049] The preferred embodiments of the present disclosure have been described above, but the present disclosure is not limited to the above embodiments.

Examples

[0050] Hereinafter, the present invention will be described in more detail by way of examples, but the present disclosure is not limited to these examples.

[0051] (Example 1) (1) Preparation of Material 1 for Chemical Looping System 0.3137 g of cobalt(II) nitrate hexahydrate (manufactured by Kanto Chemical), 0.1876 g of indium(III) nitrate trihydrate (manufactured by Kanto Chemical), and 2.000 g of cerium(IV) oxide (catalyst reference catalyst CEO-01 of the Catalysis Society) were dissolved in 25 mL of pure water and stirred uniformly to obtain a precursor solution. At this time, urea water was prepared in parallel with the stirring of the precursor solution (0.4758 g of urea was dissolved in 15 mL of pure water). Next, while stirring the precursor solution at room temperature, the urea water was slowly dropped. After dropping, heat treatment was carried out at 95 °C for 16 hours in an oil bath. After heat treatment, the precipitate was washed with pure water while performing vacuum filtration. The obtained precipitate was dried together with the filter paper in an oven at 120 °C for 5 hours. After drying, the powder was calcined in the air at 500 °C for 2 hours to obtain an oxidized form of Material 1 for the chemical looping system (heating rate 5 °C / min).

[0052] (2) Pretreatment The obtained oxidized form was subjected to a reduction treatment to obtain a reduced form of Material 1 for the chemical looping system. Specifically, the oxidized form was filled into a reactor, and hydrogen gas was passed through at a flow rate of 60 Ncc / min under atmospheric pressure, heated to 600 °C, and subjected to a reduction treatment for 60 minutes.

[0053] (3) Methanol production test After purging the inside of the reactor after the reduction treatment, while maintaining the temperature at 350 °C, H 2 / CO 2 (molar ratio 3 / 1) mixed gas was passed through at a flow rate of 80 Ncc / min for 180 minutes. An ice-cooled trap was installed at the outlet of the reactor to collect the product, and analysis was performed using a GF-FID to determine the methanol yield (mmol / g). The methanol yield indicates the amount of methanol (mmol) per unit mass (g) of the oxidized form of the material for the chemical looping system. The results are shown in Table 1.

[0054] (Example 2) (1) Preparation of Material 2 for the chemical looping system 0.2573 g of copper(II) nitrate trihydrate (manufactured by Kanto Chemical), 0.1876 g of indium(III) nitrate trihydrate (manufactured by Kanto Chemical), and 2.000 g of cerium(IV) oxide (catalyst reference catalyst CEO-01 of the Catalysis Society) were dissolved in 25 mL of pure water and stirred uniformly to obtain a precursor solution. At this time, urea solution was prepared in parallel with the stirring of the precursor solution (0.4758 g of urea was dissolved in 15 mL of pure water). Next, while stirring the precursor solution at room temperature, the urea solution was slowly added dropwise. After the addition, heat treatment was carried out at 95 °C for 48 hours in an oil bath. After the heat treatment, the precipitate was washed with pure water while performing vacuum filtration. The obtained precipitate was dried together with the filter paper in an oven at 120 °C for 5 hours. After drying, the powder was calcined in air at 500 °C for 2 hours to obtain an oxidized form of Material 2 for the chemical looping system (heating rate 5 °C / min).

[0055] (2) Pretreatment and methanol production test The pretreatment and methanol production test were carried out in the same manner as in Example 1 except that the oxidized form of Material 2 for the chemical looping system was used. The results are shown in Table 1.

[0056] (Example 3) (1) Preparation of Material 3 for the chemical looping system 0.3134 g of nickel(II) nitrate hexahydrate (manufactured by Kanto Chemical), 0.1876 g of indium(III) nitrate trihydrate (manufactured by Kanto Chemical), and 2.000 g of cerium(IV) oxide (catalyst reference catalyst CEO-01 of the Catalysis Society) were dissolved in 25 mL of pure water and stirred uniformly to obtain a precursor solution. At this time, urea solution was prepared in parallel with the stirring of the precursor solution (0.4758 g of urea was dissolved in 15 mL of pure water). Next, while stirring the precursor solution at room temperature, the urea solution was slowly added dropwise. After the addition, heat treatment was carried out at 95 °C for 16 hours in an oil bath. After the heat treatment, the precipitate was washed with pure water while performing vacuum filtration. The obtained precipitate was dried together with the filter paper in an oven at 120 °C for 5 hours. After drying, the powder was calcined in air at 500 °C for 2 hours to obtain an oxidized form of Material 3 for the chemical looping system (heating rate 5 °C / min).

[0057] (2) Pretreatment and methanol production test The pretreatment and methanol production test were carried out in the same manner as in Example 1, except that the oxidized form of Material 3 for the chemical looping system was used. The results are shown in Table 1.

[0058] (Example 4) (1) Preparation of Material 4 for the chemical looping system 0.2573 g of copper nitrate trihydrate (manufactured by Kanto Chemical), 0.1568 g of cobalt nitrate hexahydrate (manufactured by Kanto Chemical), and 2.000 g of cerium oxide (reference catalyst CEO-01 of the Catalysis Society) were dissolved in 25 mL of pure water and stirred uniformly to obtain a precursor solution. At this time, parallel to the stirring of the precursor solution, urea water was prepared (0.4758 g of urea was dissolved in 15 mL of pure water). Then, while stirring the precursor solution at room temperature, the urea water was slowly dropped. After dropping, heat treatment was carried out at 95 °C for 48 hours in an oil bath. After the heat treatment, the precipitate was washed with pure water while performing vacuum filtration. The obtained precipitate was dried together with the filter paper in an oven at 120 °C for 5 hours. After drying, the powder was calcined in the air at 500 °C for 2 hours to obtain the oxidized form of Material 4 for the chemical looping system (heating rate 5 °C / min).

[0059] (2) Pretreatment and methanol production test The pretreatment and methanol production test were carried out in the same manner as in Example 1, except that the oxidized form of Material 4 for the chemical looping system was used. The results are shown in Table 1.

Table 1

[0060] (Confirmation Tests 1 to 4) After the methanol production tests of Examples 1 to 4, hydrogen was circulated through the reactor to perform a reduction treatment. After the reduction treatment, when the methanol production test was carried out again, a methanol yield similar to the values shown in Table 1 was obtained. From this result, it was confirmed that Materials 1 to 4 of Examples 1 to 4 can be suitably used as materials for the chemical looping system.

Explanation of symbols

[0061] 1…Chemical looping system, 2…Oxidation treatment unit, 4…Reduction treatment unit, 6…Circulation path, 8…Reactor.

Claims

1. 1. A method for producing methanol, comprising: an oxidation step of contacting a first material comprising an oxygen carrier with carbon dioxide and hydrogen to obtain a second material comprising an oxide of the oxygen carrier and methanol.

2. The method according to claim 1 , wherein the second material is subjected to a reduction treatment and reused as the first material.

3. The method of claim 1 further comprising a reduction step of contacting the second material with hydrogen to reduce the oxide to obtain the first material and water.

4. The method according to claim 3 , wherein the oxidation step and the reduction step are carried out alternately.

5. The oxidation process is performed by a manufacturing apparatus including an oxidation processing unit that performs the oxidation step and a reduction processing unit that performs the reduction step, The second material generated in the oxidation step is supplied from the oxidation treatment unit to the reduction treatment unit, The first material generated in the reduction step is supplied from the reduction treatment unit to the oxidation treatment unit. The method according to claim 3.

6. The method according to claim 1 , wherein the first material contains active sites for the hydrogenation reaction of carbon monoxide.

7. The method according to claim 1 , wherein the first material contains active sites for a hydrogenation reaction of carbon dioxide.

8. The method according to claim 1 , wherein the oxygen carrier comprises cobalt and at least one selected from the group consisting of copper and indium.

9. The method according to claim 1 , wherein the oxygen carrier comprises indium and at least one selected from the group consisting of cobalt, copper, and nickel.

10. The method according to claim 8 or 9, wherein the first material comprises a support and the oxygen carrier supported on the support.

11. The method according to claim 1 , wherein the reaction temperature in the oxidation step is 280° C. or higher and 400° C. or lower.

12. an oxidation treatment section that brings a first material including an oxygen carrier into contact with carbon dioxide and hydrogen to produce a second material including an oxide of the oxygen carrier and methanol; a reduction treatment section that brings the second material into contact with hydrogen to reduce the oxide and generate the first material and water; a first transport means for transporting the second material from the oxidation treatment section to the reduction treatment section; a second transport means for transporting the first material from the reduction treatment section to the oxidation treatment section; A manufacturing apparatus comprising:

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