KR20180106884A - Carbon dioxide fixation device and fuel producing system - Google Patents

Abstract

According to the embodiment, provided is a carbon dioxide immobilization device having a non-aqueous phase and a water phase. The non-aqueous phase includes an ionic liquid, an enzyme body, and a mediator. The enzyme body catalyzes a reduction reaction of carbon dioxide or a reduction product thereof. The mediator acts as a reducing agent or a coenzyme in the reduction reaction. In the non-aqueous phase, the reaction product is produced by the reduction reaction. The water phase contains an extract containing water. In the aqueous phase, the reaction product is supplied from the non-aqueous phase.

Description

TECHNICAL FIELD [0001] The present invention relates to a carbon dioxide immobilization device and a fuel production system,

An embodiment of the present invention relates to a carbon dioxide immobilization apparatus and a fuel production system.

The consumption of coal, which continues to increase year by year, causes a rise in the atmospheric carbon dioxide (CO ₂ ) concentration, which is a major cause of global warming. In the natural world, and is converted to CO ₂ of around 100 billion tons per year by the photosynthesis in the biomass. However, it was let alone industrial revolution, the result of natural photosynthesis to increase the CO ₂ emissions each year since continued, the rate of CO ₂ emissions, according to magazine rate is now to convert CO ₂ into biomass.

Therefore, as one of measures against global warming, it has become necessary to capture and store CO ₂ , which is a cause gas thereof.

Even so far, chemical absorption and separation of CO ₂ by inorganic chemicals (for example, alkaline solutions such as amines), physical absorption and separation of CO ₂ by absorption liquids such as methanol and polyethylene glycol, and membrane separation methods such as polymer membranes and ceramics membranes , there is a take various daechaekbeop such as separation of CO _2, activated carbon or a zeolite such as physical absorption of CO ₂ by the porous absorbing material of the separation, one support to the CO ₂ compression (compression) embedded in the sea floor. Among the carbon dioxide capture and storage technologies (CCS), for example, a technology for separating and recovering CO ₂ generated from a thermal power plant, transporting it, storing it in a basement or a seabed is promoted have. However, problems such as cost for separating and recovering CO ₂ have been proposed.

A problem to be solved by the present invention is to provide a carbon dioxide immobilization apparatus for immobilizing carbon dioxide with high efficiency and a fuel production system using the same.

According to the embodiment, there is provided a carbon dioxide immobilization apparatus having a non-aqueous phase and a water phase. The non-aqueous phase includes an ionic liquid, an enzyme body, and a mediator. The enzyme body catalyzes the reduction reaction of carbon dioxide or its reduction product. The mediator acts as a reducing agent or a coenzyme in the reduction reaction. In the non-aqueous phase, a reaction product is produced by the reduction reaction. The water phase contains an extract containing water. In the water phase, the reaction product is supplied from the non-aqueous phase.

According to another embodiment, there is provided a fuel production system including a fuel generation portion, a carbon dioxide supply portion, and an extractor recovery portion. The fuel generating section includes the carbon dioxide immobilization apparatus according to the above embodiment. The carbon dioxide supply part supplies carbon dioxide to the fuel generation part. The extractor recovery unit recovers the reaction product from the fuel generator.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic view of an example carbon dioxide immobilization apparatus according to an embodiment; FIG.
2 is a schematic view of another example of the carbon dioxide immobilization apparatus according to the embodiment mode.
3 is a schematic view of an example carbon dioxide immobilization apparatus according to another embodiment of the present invention.
Fig. 4 is a schematic view of another carbon dioxide immobilizer according to another embodiment of the present invention. Fig.
5 is a schematic view of a modified example of the carbon dioxide immobilization apparatus shown in Fig.
6 is a schematic view of another modified example of the carbon dioxide immobilization apparatus shown in Fig.
7 is a schematic view showing another example of the carbon dioxide immobilization apparatus according to another embodiment of the present invention.
8 is a schematic view showing another example of the carbon dioxide immobilization apparatus according to another embodiment of the present invention.
Figs. 9A, 9B and 9C are schematic views showing a state in which a member included in the carbon dioxide immobilization apparatus shown in Fig. 8 is being manufactured. Fig.
10 is a schematic view of a carbon dioxide immobilizer according to still another embodiment of the present invention.
11A and 11B are schematic views of single cells constituting an example of the stacked carbon dioxide immobilization apparatus according to the embodiment.
12 is a schematic view of an example of the stacked carbon dioxide immobilization apparatus according to the embodiment.
13 is a diagram showing an example fuel production system according to the embodiment.
Fig. 14 is a schematic view of a modified example of the carbon dioxide immobilizer according to the embodiment of the present invention.

Recently, in addition to the prevention of global warming, a realization of a sustainable society aimed As a next step, the capture of CO ₂ and not only stores, biorefinery to actively convert from CO ₂ to useful materials such as fossil fuels, biomass , And the development and establishment of bioprocesses such as the immobilization of CO ₂ .

In recent years, techniques for gelation and film formation of ionic liquids capable of absorbing and separating CO ₂ with high efficiency have been established. On the other hand, research has been actively conducted to convert captured CO ₂ into a fuel that is actively useful by two kinds of conversion methods of electrochemical conversion and photochemical conversion. As the electrochemical conversion method, for example, by using a material modified with spherical copper nano-particles of graphene in the form of spikes as an electrode and a catalyst without using a noble metal or a rare metal, it is possible to obtain a high selectivity from carbon dioxide It has been reported that ethanol can be produced with high Faraday efficiency. This method is an extremely attractive method for producing chemical fuels because it can produce chemical fuels by using electric energy obtained from wind power generation or solar power generation, and is also a production method which has attracted much attention from the necessity of energy conversion and storage . However, since CO ₂ remains in water and does not dissolve, production of ethanol at a high concentration is difficult.

The enzyme conversion method is one of clean, high-efficiency fuel production methods capable of selectively converting CO ₂ into fuel under mild conditions, and has been attracting attention in recent years. However, current enzyme conversion methods have problems such as loss of intermediate products in the production of fuel (methanol) by multistage enzymatic reaction. In addition, the purity and concentration of methanol produced is low, and various problems such as inactivation and outflow of the enzyme are encountered. As one of the root causes of these problems, it is conceivable that CO _{2, which} is a raw material for producing fuel, has a low solubility in an aqueous solution as a reaction solvent, like an electrochemical method.

(First Embodiment)

According to the first embodiment, there is provided a carbon dioxide immobilization apparatus having a non-aqueous phase and a water phase. The non-aqueous phase includes one or more ionic liquids, one or more enzyme substances, and one or more mediators. The water phase contains an extract.

The non-aqueous phase and the aqueous phase are contacted through, for example, one or more porous films or separators. Alternatively, the non-aqueous phase and the aqueous phase may be in direct contact with each other.

Carbon dioxide (CO ₂ ) is supplied to the non-aqueous phase in the carbon dioxide immobilization apparatus according to the embodiment. By using an ionic liquid as the medium of non-aqueous phase, CO ₂ can be selectively and efficiently absorbed into the non-aqueous phase.

The source of carbon dioxide is, for example, a gas containing carbon dioxide. The source of the carbon dioxide is not particularly limited as long as it is a gas containing carbon dioxide. For example, atmospheric gas, gas generated from a thermal power plant, exhaust gas, gas from dry ice, gas from a carbon dioxide gas cylinder, and the like can be used as a source of carbon dioxide.

Further, the carbon dioxide immobilization apparatus according to the embodiment may further include a mechanism for bringing the gas containing the carbon dioxide into contact with, for example, the non-aqueous phase. Alternatively, in the apparatus, for example, the non-aqueous phase may be exposed to the atmosphere. Thus, the design of the carbon dioxide immobilization apparatus can be appropriately set in accordance with the source of the gas including the carbon dioxide as the reactant.

The carbon dioxide immobilizer may be provided with a mechanism for supplying a gas including carbon dioxide to the non-aqueous phase while being pressurized at a pressure higher than, for example, normal pressure (0.101325 MPa = 1 atm). By increasing the pressure of the gas, that is, the pressure of the carbon dioxide, the supply speed of the carbon dioxide to the non-aqueous phase can be improved.

The one or more enzyme bodies contained in the non-aqueous phase each contain at least one enzyme. As will be described later in detail, carbon dioxide supplied to the non-aqueous phase is reduced by the enzyme reaction, for example, fuel is produced. Therefore, in the carbon dioxide immobilization apparatus, the portion including the non-aqueous phase may be referred to as a carbon dioxide reducing reaction portion.

The at least one mediator included in the non-aqueous phase is a mediator of the reduction reaction catalyzed by the enzyme body. Specifically, the mediator acts as a reducing agent or a coenzyme in the reduction reaction. In the reduction reaction, the mediator reduces the carbon dioxide or its reduction product, and the mediator itself is oxidized.

When the mediator participates in the reduction reaction as a reducing agent or a coenzyme, electrons can move from the mediator to the reaction site of the reduction reaction. The electrons transferred to the reaction site can be used for the reduction reaction. Also, as the mediator emits electrons, the mediator can be oxidized.

Further, the enzyme reaction for reducing carbon dioxide may be a multi-step reaction. In this case, an enzyme body that catalyzes an enzyme reaction that further reduces the reduction product of carbon dioxide is included in the non-aqueous phase. Through a multiple-stage reduction reaction, carbon dioxide can be reduced to the final product.

In addition, the enzyme bodies included in the non-aqueous phase may include catalysing the reduction reaction of an oxidized mediator (for example, oxidized form of a mediator). The enzyme body that catalyzes the reduction reaction of oxidized mediator and the enzyme body that catalyzes the reduction reaction of carbon dioxide may be other enzyme bodies. Alternatively, the enzyme body for reducing oxidized mediator and the enzyme body for reducing carbon dioxide may be the same enzyme body. For example, both an enzyme catalyzing the reduction reaction of the mediator and an enzyme catalyzing the reduction reaction of the carbon dioxide can be contained in one enzyme body. Likewise, the enzyme body catalyzing the reduction reaction of the oxidized mediator and the enzyme body catalyzing the reduction reaction of the reduction product of carbon dioxide may be other enzyme bodies, or both may be the same enzyme body. For example, both of the enzyme catalyzing the reduction reaction of the mediator and the enzyme catalyzing the reduction reaction of the reduction product of carbon dioxide can be contained in one enzyme body.

The reaction product produced in the non-aqueous phase is supplied to the water phase. The extract containing the water phase selectively extracts the reaction products produced in the non-aqueous phase. According to one example of the aqueous phase extract, the final product in the multistage enzyme reaction of carbon dioxide is selectively extracted and recovered. Therefore, in the carbon dioxide immobilization apparatus, the water phase can be referred to as a fuel recovery section.

Further, the carbon dioxide immobilization apparatus according to the embodiment can include the carbon dioxide reduction reaction unit that generates the fuel by reducing the carbon dioxide as described above, and the fuel recovery unit that recovers the generated fuel. Therefore, The device may also be referred to as a fuel producing device.

The fixation of carbon dioxide as referred to herein means conversion of carbon dioxide to carbon compounds by a chemical reaction. Carbon dioxide, which is the cause of global warming, can be converted to a carbon, gas, liquid or solid state by a chemical reaction, thereby reducing carbon dioxide. Further, as the carbon compound, carbon dioxide can be used as a resource, for example, by obtaining a useful substance such as a fuel.

In addition, the conversion of carbon dioxide into carbon compounds by the chemical reaction includes carbon dioxide reduction.

In the carbon dioxide immobilization apparatus according to the embodiment, a site where a reaction product (carbon dioxide or a reduction product thereof) is reduced to generate a reaction product and a site where a reaction product (carbon compound as a reduction product of carbon dioxide) Respectively. Therefore, it is difficult for the reactants to mix with the reaction products, and the reaction products can be recovered with a small amount of impurities.

Further, in the carbon dioxide immobilization apparatus according to the embodiment, in order to extract the reaction product (for example, fuel) from the non-aqueous phase containing the reaction field, the aqueous phase is desorbed so that the equilibrium of the enzyme reaction of the fuel production is shifted toward the reaction product side. can do. Further, by extracting the reaction product from the non-aqueous phase, the loss of the reaction product is reduced. As a result, the yield of the resulting reaction product (e.g., fuel) can be increased.

As described above, the carbon dioxide immobilization apparatus according to the embodiment exerts a high performance for immobilizing carbon dioxide by efficiently performing a reaction for reducing carbon dioxide or a reduction product thereof to a reaction product such as methanol. Therefore, CO ₂ emission can be suppressed, and a compound useful as a fuel or the like can be produced.

According to the first aspect of the carbon dioxide immobilization apparatus according to the embodiment, the non-aqueous phase may include a first non-aqueous phase, a second non-aqueous phase, and a third non-aqueous phase, and the aqueous phase includes a first aqueous phase and a second aqueous phase Three awards may be included. In other words, the carbon dioxide immobilization apparatus of this embodiment can include a plurality of non-aqueous phase and a plurality of aqueous phase.

The first non-aqueous phase is supplied with carbon dioxide. In the first non-aqueous phase, the first reaction product is produced by the reduction reaction of the supplied carbon dioxide. According to one example, the first reaction product is formic acid.

As used herein, formic acid means any form of formate anion (HCOO ^- ), formate acid (HCOOH) in which a proton is bonded to a formic acid anion, or formate salt in which a cation is bonded to a formic acid anion . The formic acid in the following description also includes any of the above-mentioned forms. In addition, other compounds such as anions, acids, and salts may be used.

In the first water phase, the first reaction product is supplied from the first non-aqueous phase. Further, the first water phase feeds the first reaction product to the second non phase phase.

In the second non-aqueous phase, the first reaction product is supplied. In the second non-aqueous phase, the second reaction product is produced by the reduction reaction of the supplied first reaction product. According to one example, the second reaction product is formaldehyde.

In the second water phase, the second reaction product is supplied from the second non-aqueous phase. Further, the second water phase feeds the second reaction product to the third non phase phase.

In the third non-aqueous phase, the second reaction product is supplied from the second aqueous phase. In the third non-aqueous phase, the third reaction product is produced by the reduction reaction of the supplied second reaction product. According to one example, the third reaction product is methanol. The third reaction product produced in the third non-aqueous phase is supplied to the third water phase.

In the third water phase, the third reaction product is supplied from the third water phase. Thus, a third reaction product is obtained.

In this mode, carbon dioxide is reduced to a final product (fuel) by a three-step enzyme reaction in the first to third non-aqueous phase. That is, the first reaction product and the second reaction product are intermediate products of the three-step reaction, and the third reaction product is the final product.

Each of the first to third non-aqueous phase may include one or more ionic liquids, one or more enzyme substances, and one or more mediators. The first to third non-aqueous phase may be different from each other in the kind and number of ion liquid, enzyme body and mediator which they contain.

The enzyme body included in the first non-aqueous phase includes an enzyme that catalyzes a reduction reaction in which carbon dioxide is reduced to produce a first reaction product. Further, the mediator included in the first non-aqueous phase serves as a reducing agent or a coenzyme in the reduction reaction for producing the first reaction product.

The enzyme body included in the second non-aqueous phase includes an enzyme that catalyzes a reduction reaction in which the first reaction product is reduced to produce a second reaction product. In addition, the mediator included in the second non-aqueous phase serves as a reducing agent or a coenzyme in the reduction reaction for producing the second reaction product.

Likewise, the enzyme bodies included in the third non-aqueous phase include enzymes that catalyze a reduction reaction that reduces the second reaction product to produce a third reaction product. Further, the mediator included in the third non-aqueous phase acts as a reducing agent or a coenzyme in the reduction reaction for producing the third reaction product.

The enzyme body included in the first non-aqueous phase may include an enzyme body that catalyzes the reduction reaction of the oxidized product of the mediator. Such an enzyme body may include an enzyme that catalyzes a reduction reaction of the oxidant of the mediator. The enzyme body that catalyzes the reduction reaction for reducing carbon dioxide to the first reaction product and the enzyme body that catalyzes the reduction reaction of the oxidant of the mediator may be the same enzyme or different enzyme bodies.

The enzyme body included in the second non-aqueous phase may include an enzyme body that catalyzes the reduction reaction of the oxidized product of the mediator. Such an enzyme body may include an enzyme that catalyzes a reduction reaction of the oxidant of the mediator. The enzyme body which catalyzes the reduction reaction for reducing the first reaction product to the second reaction product and the enzyme body which catalyzes the reduction reaction of the oxidation product of the mediator may be the same or different enzyme bodies.

The enzyme body included in the third non-aqueous phase may include an enzyme body that catalyzes the reduction reaction of the oxidized product of the mediator. Such an enzyme body may include an enzyme that catalyzes a reduction reaction of the oxidant of the mediator. The enzyme body that catalyzes the reduction reaction for reducing the second reaction product to the third reaction product and the enzyme body that catalyzes the reduction reaction of the oxidant of the mediator may be the same enzyme or different enzyme bodies.

In this embodiment, since the first reaction product produced in the first non-aqueous phase is selectively extracted by the extract liquid contained in the first aqueous phase, the equilibrium of the reduction reaction of carbon dioxide in the first non- As shown in FIG. Also, in the second non-aqueous phase, since the first reaction product as a substrate is supplied from the first aqueous phase and the produced second reaction product is selectively extracted by the extract liquid contained in the second aqueous phase, The equilibrium of the reaction can be shifted toward the second reaction product side. In the third non-aqueous phase, since the second reaction product as the substrate is supplied from the second aqueous phase and the produced third reaction product is selectively extracted and recovered by the extract liquid contained in the third aqueous phase, The equilibrium of the reduction reaction can be shifted toward the third reaction product side.

Thus, the equilibrium of the three-step reaction in which carbon dioxide is reduced to the third reaction product as the final product can be shifted to the end product side in each reaction step, so that the final product can be recovered at a high yield. In addition, since the reactant (carbon dioxide) and the intermediate product (first and second reaction products) are difficult to be incorporated into the final product (third reaction product), a high-purity final product can be obtained. In addition, in each step in which the intermediate product in the first non-aqueous phase and the second non-aqueous phase is produced, the first and second aqueous phase recover the respective intermediate products, that is, the first reaction product and the second reaction product Therefore, the loss of the intermediate product is suppressed.

Further, in the modification of the first embodiment, for example, a two-step enzyme reaction in which carbon dioxide is reduced to two stages as the final product can be employed instead of the three-stage enzyme reaction. In this case, the non-award includes the first non-award and the second non-award. In the first non-aqueous phase, carbon dioxide is supplied, and the first reaction product is produced by the reduction reaction of the carbon dioxide. In the second non-aqueous phase, the first reaction product is supplied, and the second reaction product is produced by the reduction reaction of the first reaction product. The second reaction product produced in the second non-aqueous phase is supplied to the water phase.

In this variation, only the first reaction product is an intermediate product. In addition, the second reaction product is the final product. Therefore, the second reaction product is extracted and recovered by the extract liquid contained in the second water phase. Except for this point, the configuration of this modified example is the same as that of the first embodiment, and a description thereof will be omitted.

The reaction for reducing carbon dioxide may be a multistage reaction involving four or more steps if necessary. Depending on the number of reaction steps included in the multistage reaction, the number of non-aqueous phase and water phase can be appropriately changed. In addition, a substrate other than carbon dioxide and an intermediate product (reduction product of carbon dioxide) may be included in each of the non-aqueous phases as required.

The first embodiment of the carbon dioxide immobilization apparatus may be of a flow type or a batch type.

In the flow type, the supply of carbon dioxide to the first non-aqueous phase, the supply of the reaction product from each non-aqueous phase to the next aqueous phase, and the supply of the reaction product from each aqueous phase to the next non-aqueous phase are successively performed.

In the batch mode, the supply of reaction products from at least each water phase to the next non-aqueous phase is discontinuously performed. For example, when the three-step reaction is employed, the first reaction product produced by reducing the carbon dioxide supplied to the first non-aqueous phase is supplied to the first aqueous phase, and the first reaction product is recovered to the first phase . ≪ / RTI > Likewise, the second reaction product produced at the second non-aqueous phase is temporarily stored in the second water phase after being supplied to the second water phase. In order to form a batch, for example, a mechanism for controlling the flow of the extract liquid may be provided in each of the first and second aquifers.

According to the second embodiment of the carbon dioxide immobilization apparatus according to the embodiment, the non-aqueous phase may include a first non-aqueous phase, a second non-aqueous phase, and a third non-aqueous phase. That is, the carbon dioxide immobilization apparatus of this embodiment can include a plurality of non-water-immobilized carbon dioxide immobilization apparatuses. The first non-aqueous phase is supplied with carbon dioxide. In the first non-aqueous phase, the first reaction product is produced by the reduction reaction of the supplied carbon dioxide. In the second non-aqueous phase, the first reaction product is supplied. In the second non-aqueous phase, the second reaction product is produced by the reduction reaction of the supplied first reaction product. In the third non-aqueous phase, the second reaction product is supplied. In the third non-aqueous phase, the third reaction product is produced by the reduction reaction of the supplied second reaction product. The third reaction product produced in the third non-aqueous phase is supplied to the water phase.

In this mode, carbon dioxide is reduced to a final product (fuel) by a three-step enzyme reaction in the first to third non-aqueous phase. That is, the first reaction product and the second reaction product are intermediate products of the three-step reaction, and the third reaction product is the final product.

Each of the first to third non-aqueous phase may include one or more ionic liquids, one or more enzyme substances, and one or more mediators. The first to third non-aqueous phase may be different from each other in the kind and number of ion liquid, enzyme body and mediator which they contain.

The enzyme body included in the first non-aqueous phase includes an enzyme that catalyzes a reduction reaction in which carbon dioxide is reduced to produce a first reaction product. Further, the mediator included in the first non-aqueous phase serves as a reducing agent or a coenzyme in the reduction reaction for producing the first reaction product.

The enzyme body included in the second non-aqueous phase includes an enzyme that catalyzes a reduction reaction in which the first reaction product is reduced to produce a second reaction product. In addition, the mediator included in the second non-aqueous phase serves as a reducing agent or a coenzyme in the reduction reaction for producing the second reaction product.

Likewise, the enzyme bodies included in the third non-aqueous phase include enzymes that catalyze a reduction reaction that reduces the second reaction product to produce a third reaction product. Further, the mediator included in the third non-aqueous phase acts as a reducing agent or a coenzyme in the reduction reaction for producing the third reaction product.

The enzyme body included in the first non-aqueous phase may include an enzyme body that catalyzes the reduction reaction of the oxidized product of the mediator. Such an enzyme body may include an enzyme that catalyzes a reduction reaction of the oxidant of the mediator. The enzyme body that catalyzes the reduction reaction for reducing carbon dioxide to the first reaction product and the enzyme body that catalyzes the reduction reaction of the oxidant of the mediator may be the same enzyme or different enzyme bodies.

The enzyme body included in the second non-aqueous phase may include an enzyme body that catalyzes the reduction reaction of the oxidized product of the mediator. Such an enzyme body may include an enzyme that catalyzes a reduction reaction of the oxidant of the mediator. The enzyme body which catalyzes the reduction reaction for reducing the first reaction product to the second reaction product and the enzyme body which catalyzes the reduction reaction of the oxidation product of the mediator may be the same or different enzyme bodies.

The enzyme body included in the third non-aqueous phase may include an enzyme body that catalyzes the reduction reaction of the oxidized product of the mediator. Such an enzyme body may include an enzyme that catalyzes a reduction reaction of the oxidant of the mediator. The enzyme body that catalyzes the reduction reaction for reducing the second reaction product to the third reaction product and the enzyme body that catalyzes the reduction reaction of the oxidant of the mediator may be the same enzyme or different enzyme bodies.

In the carbon dioxide immobilization apparatus of the second embodiment, the first reaction product produced at the first non-aqueous phase is directly supplied to the second non-aqueous phase. Also, the second reaction product produced at the second non-aqueous phase is directly fed to the third non-aqueous phase.

Thus, the intermediate product (the first reaction product, the second reaction product) is supplied to the non-aqueous phase (second non-aqueous phase, third non-aqueous phase) containing the reaction zone of the next reaction stage in the multistage reaction for reducing the carbon dioxide When, it does not go through the prime minister. Therefore, the loss of the intermediate product can be reduced.

Further, in the modification of the second embodiment, for example, a two-step enzyme reaction in which carbon dioxide is reduced to a final product can be employed instead of the three-step enzyme reaction. In this case, the non-award includes the first non-award and the second non-award. In the first non-aqueous phase, carbon dioxide is supplied, and the first reaction product is produced by the reduction reaction of the carbon dioxide. In the second non-aqueous phase, the first reaction product is supplied, and the second reaction product is produced by the reduction reaction of the first reaction product. The second reaction product produced in the second non-aqueous phase is supplied to the water phase.

In this variation, only the first reaction product is an intermediate product. In addition, the second reaction product is the final product. Therefore, the second reaction product is extracted and recovered by the extract liquid contained in the second water phase. Except for this point, the configuration of this modified example is the same as that of the second embodiment, and a description thereof will be omitted.

In the same manner as in the first embodiment, the reaction for reducing carbon dioxide, if necessary, may be a multistage reaction including four or more steps. Depending on the number of reaction steps included in the multistage reaction, the number of non-aqueous phase and water phase can be appropriately changed. In addition, a substrate other than carbon dioxide and an intermediate product (reduction product of carbon dioxide) may be included in each of the non-aqueous phases as required.

Next, details of the non-aqueous phase and the aqueous phase in the carbon dioxide immobilizing apparatus according to the embodiment will be described.

<Non-awarded>

The non-aqueous phase includes an ionic liquid, an enzyme body, and a mediator.

[Ionic liquid]

As a medium for non-aqueous release, it is preferable to use a material having the following characteristics:

(1) High ability to absorb and separate CO ₂

(2) The vapor pressure is low.

(3) High thermal stability

(4) High conductivity

(5) The potential window is wide.

(6) High chemical stability

(7) a protein stabilizing agent.

No particular limitation is imposed on a non-water-absorbing material having the above-mentioned main characteristics, but it is preferable to use an ionic liquid as a non-water-absorbing medium. The ionic liquid is used as a non-aqueous medium in view of low vapor pressure (close to zero), wide potential window, high absorption of specific substances such as carbon dioxide, high heat stability and high conductivity .

Ionic liquids with high solubility in CO ₂ can absorb a large amount of carbon dioxide. For example, by using such an ionic liquid as a non-water-soluble medium, it is possible to efficiently supply CO ₂ as a reactant with a non-aqueous phase containing an enzyme body as a place for a CO ₂ reduction reaction. When an ionic liquid is used as the medium of the non-aqueous phase, the amount of CO ₂ absorption increases with the pressurization. For example, a _{1% (CO 2 mole% in} ionic liquid) or more ionic liquid capable of absorbing _{60% (CO 2 mole% in} ionic liquid) or more CO ₂ When the pressure, if the pressure to 0.1MPa to 6MPa Is preferably used.

As described above, the ionic liquid has high conductivity and excellent ion conductivity and electron conductivity. Since excellent ion conductivity and electron conductivity favor the electron transfer in the non-aqueous phase, it is possible to produce the product (for example, fuel) rapidly and efficiently. For example, when the mediator acts as a reducing agent or a coenzyme in an enzyme reaction in an enzyme body, electrons are easily transferred from the mediator to the redox site of the enzyme, and the enzyme reaction is promoted. Further, even when the mediator is regenerated or reduced by the action of the electrode as described later, since the movement of electrons from the electrode to the mediator is promoted, regeneration and reduction can be performed with high efficiency.

The ionic liquid is also called a designer liquid, and the anion and the cation can be freely designed (designed) by appropriately selecting the anion and the cation in accordance with the purpose.

Representative cations of ionic liquids include, for example, imidazolium, ammonium, phosphonium, and pyridinium.

Other representative cations of ionic liquids include, for example, 1-methyl-3-alkylimidazolium, 1,3-bis [3-methylimidazolium-1-yl] alkane, poly (diallyldimethylammonium), metal (M ⁺ ) tetraglyme, .

Typical anion of the ionic liquid is, for example, bis (trifluoromethanesulfonyl) imide ([Tf 2 N] -, [TFSI] -, or ^{[TFSA] -), tetrafluoroborate (} [BF 4] -), hexafluorophosphate ([PF 6] ^- ), dicyanoamine ([DCA] ^- ), and the like.

Other representative anions of ionic liquids include halides, formate, nitrate, hydrogen sulfate, heptafluorobutyrate, thiocyanate, tris (pentafluoroethyl) trifluorophosphate, dicyanamide, polyphosphonic acid, tetrachloroferrate and trifluoromethanesulfonate ([TfO] ^- ) .

An ionic liquid can be roughly divided into a nonpolar ionic liquid and a polar ionic liquid. Generally, the nonpolar ionic liquid is a hydrophobic ionic liquid and the polar ionic liquid is a hydrophilic ionic liquid.

On the other hand, a hydrophilic polar ionic liquid can also be distinguished as a protic ionic liquid and an aprotic ionic liquid. The polar ionic liquid can also be used as a reversed micelle core solution formed of a hydrophilic solvent. Further, by making the protonic ionic liquid into a gel (membrane), it can be used as a proton exchange member (PEM) like Nafion (registered trademark). The aprotic ionic liquid can be used as a refolding agent and a thermal stabilizer for proteins (enzymes).

Thus, the ionic liquid can be used by being classified depending on its characteristics.

Among the ionic liquids, it is preferable to use an imidazole-based ionic liquid. The imidazole-based ionic liquid or gel thereof not only can absorb CO ₂ with high selectivity, but also has high conductivity.

Among the hydrophobic ionic liquids, the use of imidazole-based 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide (EMIMBTI) having excellent absorption properties against CO ₂ is particularly preferable.

There are a number of EMIMBTIs, including official names, aliases, and acronyms. For example, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) amide, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide [ , 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide. As codes, EMIMIm, [emim] [( CF 3 SO 2) 2 N], [emim] [TFSI], EmimTFSI, EMIMTFSI, EmimNTf 2, EmimTf 2 N, Emim TFSI, Emim NTf 2, Emim Tf 2 N, [ C ₂ mim] [NTf ₂ ], BMIM-NTf ₂ , [C ₂ mIm ⁺ ] [TFSI ^- ], [C ₂ C ₁ im] [NTf ₂ ] In order to avoid confusion, the molecular structure is shown below.

The ionic liquid can be used in a mixture of two or more kinds in consideration of characteristics such as CO ₂ absorption characteristics, cost, toxicity, viscosity, and conductivity. For example, by using an ionic liquid having a high absorption characteristic for CO ₂ and an ionic liquid having a lower toxicity than that of the ionic liquid, a cost reduction of the material and a reduction of the toxin can be achieved.

In addition, aprotic ionic liquids in polar ionic liquids can be used as thermal stabilizers for proteins, so that polar ionic liquids can be mixed with nonpolar ionic liquids and used as non-aqueous liquids.

In addition, the cathode limit of the ionic liquid depends on the nature of the cation, and when the cation contains an electron withdrawing group, the cathode limit is widened. Therefore, it is preferable to select an ionic liquid from an ionic liquid containing a cation which absorbs carbon dioxide well and which contains an electron attracting group.

Ionic liquid, and for example, 1-methyl-3-propyl- methylimidazolium dihydrogen phosphate (PMIH 2 PO 4), polybenzimidazole (PBI), 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide, [C 8 mIm +] ^{[TFSA -] (TFSA - =} (CF 3 SO 2) 2 n -), 1-alkylimidazolium bis (trifluoromethanesulfonyl) amide, [C n ImH +] [TFSA -] (n = 4 or 8), triethyl sulfonium bis ( (trifluoromethylsulfonyl) imide ([bmim] [Tf ₂ N]), 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim] [PF ₆ ] , octyl-3-methylimidazoliumhexafluorophosphate ([ omim] [PF 6]), 1-decyl-3-methylimidazolium bis (trifluoro-methylsulfonyl) imide ([dmim] [Tf 2 N]), 1-butyl-3-methylimidazolium tetrafluoroborate ( _{[bmim] [BF 4])} , 1-dodecyl-3-methylimidazolium chloride ([dmim] [Cl]), 1-Methyl-3-octylimidazolium chloride (MOImCl), [C 2 mim] [NTf 2], [C _{6 mim] [NTf 2],} [C 8 mim] [NTf 2], [C 6 F 9 MIM] [NTf 2], 1-butyl-3-methylimidazolium bis [(trifluoromethyl) sulfonyl] imide, [ _{C 4 mim] [NTf 2]} , [C 4 mim] [PF 6], [Bmim] [PF 6] (BMIM-PF 6), [bmmim] [PF 6], [C 4 mim] [TFSI], _{IL [C 8 mim] [Tf} 2 N] (1-octyl-3-methylimidazolium bis (trifluoromethylsulfonyl) amide), IL 2 (1-ethyl-3-methylimidazolium bromide, [emim] [Br]), 1- ethyl-3-methylimidazolium trifluoromethanesulfonate ([ emim] [Tf]), 1-ethyl-3-methylimidazolium tetra-fluoroborate ([emim] [BF 4]), [emim] [AlCl 4], [emim] [H 2, _{3 F 3,3], [emim]} [CH 3 CO 2], [emim] [CF 3 SO 3], [emim] [(C 2 F 5 SO 2) 2 N], [emim] [(C 2 _{F 5 SO 2) 2 C]} , [emim] [TFA], [emim] [Ac], 1-butyl-3-methylpyridinium tetrafluoroborate ([bmpyri] [BF 4]), 1-butyl-3-methylpyrrolidinium tetrafluoroborate ( _{[bmpyrro] [BF 4])} , [bmim] [BF 4], 1-ethyl-3-methylimidazolium chloride ([emim] [Cl]), [emim] [Tf 2 N], [C 4 mim] [AC ], [P ₆₆₁₄ ] [Pro], [P ₆₆₁₄ ] [Ala], [P ₆₆₁₄ ] [Gly], [MTBDH] [TFE], [C ₂ Mime] [DCA], [C ₂ Mime] [Tf ₂ N], [C ₂ mim] [TfO], [C ₂ mim] [TCB] and the like can be used.

In addition, as the ionic liquid which can be used, for example, N- (2-Methoxyethyl-N-methylpyrrolidinium tetrafluoroborate (MEMPBF ₄ ), N- (2-Methoxyethyl- N- methylpyrrolidinium bis (trifluoromethanesulfonyl) imide N-Diethyl-N-methyl- N- (2-methoxyethyl) ammonium tetrafluoroborate (DEMEBF 4), N, N-Diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide (DEMETFSI), N N, N-trimethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide (TMPA TFSI) and N-methyl-N-propylpiperidinium bis (trifluoromethanesulfonyl) imide (PP13 TFSI).

The ionic liquid described above has the same molecular structure as EMIMBTI although its display and sign are different. In addition to the ionic liquids described above, new ionic liquids can be synthesized as needed.

It is also known that CO ₂ is physically absorbed into an ionic liquid of the imidazole ([Emim] ⁺ ) series depending on the pressure.

For example, in the case of [emim] [TFSA], [emim] [BETA], [emim] [NFBS], and [emim] [BF ₄ ], which are examples of imidazole- At atmospheric pressure (0.101325MPa = 1atm), the solubility of CO ₂ in the ionic liquid is less than about 0.1 mole fraction to less than 0.2 mole fraction. On the other hand, these ionic liquids exhibit CO ₂ solubility of mole fractions of 0.6 or more from 0.3 or more under the conditions of 40 ° C. (313 K) and 6 MPa (= 60 atm). (For example, 3 to 4 times) of CO ₂ solubility in an ionic liquid by pressurizing the pressure from an atmospheric pressure to 6 MPa at 40 ° C (313 K), depending on the kind of the imidazole-based ionic liquid. .

As described above, when the temperature is constant, the degree of physical absorption by the ionic liquid increases with the increase in the pressure of the supplied CO ₂ .

The vapor-liquid critical point of CO ₂ is 31 ° C in temperature and 7.4 MPa in pressure. When supplied to the ionic liquid used in a non-aqueous medium of the CO ₂ as a gas, it is preferred to supply the CO ₂ under the conditions CO ₂ is not a supercritical fluid. When the temperature or pressure rises from the vapor-liquid threshold, CO ₂ can become a supercritical fluid. For example, when the pressure is 7.4 MPa or less under a temperature condition of 31 캜, CO ₂ can be supplied as a gas to the non-aqueous phase.

On the other hand, the solubility of CO _{2 in} the ionic liquid depends on the temperature. In general, as the temperature rises, the solubility of CO _{2 in} the ionic liquid also decreases. Therefore, it is preferable to control the temperature to the optimum temperature according to the activity characteristics of the enzyme at each temperature.

The solubility of CO ₂ in ionic liquids is also affected by cationic species and anionic species. The solubility of CO ₂ in the ionic liquid tends to be influenced more by the anionic species than by the cationic species.

As an embodiment, in the case of an ionic liquid having the same Bmim cation, it absorbs CO ₂ well with the following anion sequence.

In the case of an ionic liquid with the same Emim cation, it absorbs CO ₂ well with the following anionic sequences.

Also, [Emim] [PF ₆ ] shows the same degree of CO ₂ absorbency as [Emim] [BF ₆ ]. On the other hand, [Emim] [DCA] has low CO ₂ absorbability compared to [Emim] [BF ₆ ] and [Emim] [PF ₆ ].

One of the reasons that CO ₂ solubility in an ionic liquid depends on the cationic species and the anionic species of the ionic liquid is in the presence of unoccupied space dispersed in the ionic liquid. The unoccupied space, which is regularly dispersed in the ionic liquid, is used as a space for accommodating CO ₂ molecules. When CO ₂ is absorbed in this unoccupied space, the unoccupied space expands (swells) with the displacement of cations and anions in the ionic liquid.

The ionic liquid with weak cohesive force between positive and negative ions tends to have a larger proportion of the unoccupied space in the ionic liquid. The higher the unoccupied space in the ionic liquid, the higher the CO ₂ absorption characteristic is obtained.

Many imidazole based ionic liquid absorb CO ₂ by physical absorption based on the above-mentioned principle.

Therefore, in the embodiments, other ionic liquids can be appropriately mixed and used, if necessary, based on the absorption characteristics of the ionic liquid having the same Emim cation to CO ₂ .

Further, in the case of an ionic liquid having the same Emim cation, the longer the perfluoroalkyl chain, the greater the effect of improving the solubility of CO ₂ . Therefore, in consideration of this effect, the perfluoroalkyl chain of the ionic liquid may be suitably designed and synthesized.

As ionic liquid to physically absorb carbon dioxide, for example, _{[C 4 mim] [Nf 2} T], [C 4 mim] [PF 6], [C 4 mim] [BF 4], [C 8 mim] [ Nf ₂ T], [C ₂ mim] [eFAP] and the like can be used.

On the other hand, the chemical absorption of CO ₂ by the ionic liquid can be performed using an ionic liquid such as an ammonia-based ionic liquid or an amino acid-based ionic liquid.

[P ₆₆₁₄ ] [Pro], [P ₆₆₁₄ ] [Ala], [P ₆₆₁₄ ] [Gly], [MTBDH] [TFE], and [N ₁₁₁₄ ] [Tf ₂ N], [MTBDH] [Im] can be used.

In addition, if the liquid is a hydrophobic ionic liquid, the solubility of water in the ionic liquid is low, so the effect of water is low. Further, when an ionic liquid is used, the following advantages can be obtained:

1) The volume expansion accompanying gas absorption is small.

2) Chemically stable over a wide temperature range

3) The risk of accidents is small due to nonflammability.

It is more preferable to immobilize the ionic liquid with the immobilizing carrier in order to improve the isolation effect of CO ₂ or to prevent problems such as leakage or leakage of the ionic liquid. For example, the ionic liquid can be immobilized by forming an ionic liquid film on the carrier material.

As the immobilization carrier for the ionic liquid, a carrier such as a porous membrane, a porous single layer material, a zeolite, a silica glass membrane, or a polymer can be used.

When a polymer is used as a carrier for an ionic liquid, the polymer / ionic liquid composite membrane, a polymer / ionic liquid fiber composite material such as a polymer / ionic liquid fiber, or the like by a casting method, an electron spinning method, composite material. As the polymer, for example, poly (vinylidene difluoride) (PVDF), poly (vinylidene difluoride) -hexafluoropropylene (PVDF-HFP) and the like can be used.

Further, by dissolving the polymer material and the ion liquid material in a solvent and spraying the same on the porous electrode material, a polymer / ion liquid film can be formed on the surface of the electrode. Since the ionic liquid can be used by being immobilized in the form of a film or a fiber, leakage of the ionic liquid due to absorption of CO ₂ by pressurization can be prevented.

As the carrier material for preparing the ionic liquid film, for example, a hydrophobic polymer material or a hydrophilic polymer material can be used. As the hydrophobic polymer material, for example, polyvinylidene fluoride (PVDF) or the like can be used. As the hydrophilic polymer material, for example, polyethylene (PE), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA) and the like can be used. Alternatively, a mixture of hydrophobic and hydrophilic polymer materials can be used. When used in combination, for example, PVDF and PTFE can be mixed and used.

In addition to the polymer material, an anodic alumina nanoporous film, porous TiO ₂ , mesoporous carbon, or the like may be used as a carrier material that can be used as an ionic liquid membrane.

The ionic liquid can also be made into an ion gel which is also gelled by a gelling agent and is also referred to as ionogel. An ion gel can also be formed to form an ion gel membrane. As the gelling agent, for example, gelatin or MOGs, hydroxypropyl methylcellulose (HPMC) can be used.

The ionic liquid can also be used as polymerized ionic liquids by polymerizing. Polymerized ionic liquids can also be formed into poly (ionic liquid) membranes.

In addition, as the ionic liquid, porous ionic liquid structures having a porous structure can be used. The porous ionic liquid structure can be obtained by cross-linking an ionic liquid in the presence of a template containing, for example, TiO ₂ , and then removing the template (for example, etching, substitution, etc.) Can be made by doing. The porous ionic liquid structure may also be prepared under the condition of free of template. As the porous ionic liquid structure usable in the embodiment, a porous ionic liquid structure capable of absorbing CO ₂ is preferable, and the kind thereof is not particularly limited.

When an ionic liquid is used as the medium of non-aqueous phase, a permeation-separation membrane (for example, a separator described later) is installed between the non-aqueous phase containing the ionic liquid and the aqueous phase for the purpose of preventing the ionic liquid from flowing out to the aqueous phase .

[Enzyme form]

The enzyme bodies contained in the non-aqueous phase include one or more enzymes. The enzyme body may be a single enzyme. Alternatively, the enzyme body includes an immobilized enzyme. Here, immobilization of an enzyme includes binding an enzyme to a carrier by a carrier binding method, enclosing the enzyme in a polymer gel or microcapsule by the inclusion method, and binding the enzymes by a cross-linking method. An enzyme body obtained by immobilizing an enzyme can be obtained, for example, by using a supporter including a complex comprising a molecular aggregate formed by a dispersant and an enzyme, microcapsules containing an enzyme, a polymer material and the like, and an enzyme supported or encapsulated by the supporter And the like. As the enzyme body, cells or microorganisms including an enzyme may also be used.

In most cases, the enzyme reaction requires water. This is due to the fact that the enzyme is a biocatalyst originally acting in water. Generally, enzymes exhibit high enzymatic activity because they become soft in water. On the contrary, in the system without water, the activity of the enzyme is markedly lowered. Therefore, in an enzyme reaction system for non-aqueous phase, the presence of an appropriate amount of water is preferable. The presence form of water depends on the form of the enzyme body, but the content of water and the form thereof are not particularly limited as long as high enzyme activity is obtained.

The enzyme body may contain water, and this water can function as an enzyme reaction field of the enzyme. Therefore, in an enzyme body containing water, the enzyme exhibits a high enzyme activity.

The enzyme bodies are dispersed in the non-aqueous medium.

In the non-aqueous phase, it includes one enzyme body, and each enzyme body may contain two or more kinds of enzymes. Alternatively, the non-aqueous phase may contain plural kinds of enzyme bodies having different kinds of enzymes. In this case, each enzyme body may contain only one enzyme or two or more enzymes.

In the case where the non-aqueous phase contains plural kinds of enzyme bodies having different kinds of enzymes, a part of the reaction products produced by the enzyme reaction in one of the enzyme bodies is the same as that of the other enzyme bodies Of the enzyme reaction. Chemical substances are rapidly exchanged between individual enzymes contained in the same system. Therefore, the reaction product produced by the enzyme reaction in one enzyme body rapidly moves to the other enzyme body, where it participates in the enzyme reaction as a substrate.

The occurrence of viruses, fungi, bacteria, seaweeds, and the like can also be prevented by placing the enzyme reaction in a non-aqueous solvent. From this point of view, it is preferable to carry out an enzyme reaction in an enzyme body dispersed in a non-aqueous medium.

The water required for the active expression of the enzyme is called "essential water". That is, it is desirable to have "essential water" around the enzyme dispersed in the non-aqueous phase. For example, when a hydrophilic enzyme is dispersed in a non-aqueous phase, a " essential water " around the enzyme is present in a thin layer of water formed from about 50 to 500 water molecules per enzyme .

Further, in the case of using an enzyme body obtained by immobilizing an enzyme, it is preferable since the following properties are expressed:

(1) a high concentration of substrate (for example, carbon dioxide, or a reduction product thereof) may be used.

(2) Stress tolerance of the enzyme is improved.

(3) Separation of the enzyme (the enzyme body) and the product becomes easy.

(4) It is easy to use the enzyme repeatedly.

(enzyme)

The enzymes that can be contained in the enzyme body are not particularly limited as long as they are enzymes that catalyze a reaction for generating a fuel by reducing carbon dioxide when a plurality of enzymes are combined. Enzymes that can be used include, for example, enzymes that function as catalysts for enzymatic reactions that reduce carbon dioxide to produce intermediates, reaction products from carbon dioxide (e.g., the reduction products of carbon dioxide as the intermediate product described above) An enzyme that functions as a catalyst for the enzyme reaction, a enzyme that captures carbon dioxide, an enzyme that reduces NAD ⁺ to NADH, and the like.

Specific examples of the enzyme include oxidoreductase-dehydrogenase such as formate dehydrogenase (FDH), metal-dependent formate dehydrogenase, formaldehyde dehydrogenase, alcohol dehydrogenase, carbonic anhydrase, glutamate dehydrogenase (GDH), and molybdenum- containing formate dehydrogenase And the like. GDH is also an example of an enzyme that reduces NAD ⁺ to NADH.

As described later, NAD ⁺ and NADH are oxidized and reduced forms of nicotinamide adenine dinucleotide, which are mediators, respectively. As a specific example of the enzyme that reduces NAD ⁺ to NADH, GDH is mentioned, but other enzymes may be used. For example, PTDH is another specific example of an enzyme that reduces NAD ⁺ to NADH. NADH / NAD ⁺ is exemplified as an example of a mediator that can be regenerated by an enzyme. Naturally, mediators that can be regenerated by an enzyme that can be contained in the enzyme body are not limited to this. The enzyme body may contain various enzymes that reduce various oxidized mediators.

Other examples include tungsten-containing formate dehydrogenase enzyme (FDH1), carbon monoxide dehydrogenase (CODH), and remodeled nitrogenase, an enzyme that reduces carbon dioxide to methane.

In addition to the above-mentioned enzymes, enzymes for converting from carbon dioxide into multi-terminal enzymatic reactions and useful substances other than fuel can be used.

Enzymes may exhibit catalytic activity under high pressure, depending on the species. For example, there are enzymes that can function under a pressure of 200 MPa. For each different type of enzyme, there may be a pressure at which the reaction rate of the enzyme-catalyzed reaction becomes maximum under certain conditions (conditions other than pressure), i.e., optimal pressure. For example, based on a certain condition (a condition other than pressure), the reaction speed is increased with increasing the pressure, and the reaction rate is maximized at the time when the optimum pressure is reached. Under higher than optimal pressure, the reaction rate is reduced. For example, the enzyme may undergo denaturation under a pressure of generally about 400 MPa or higher, so that the enzyme can not maintain its function.

As described above, the CO ₂ solubility of the ionic liquid is improved with an increase in pressure. Therefore, it is preferable to use an enzyme exhibiting catalytic activity even under the condition of increasing the pressure for promoting the CO ₂ absorption to the non-aqueous solvent. Concretely, it is preferable that the enzyme contained in the enzyme body maintains a function of catalyzing the reduction reaction of the reduction product of CO ₂ or CO ₂ even under a pressure of 400 MPa. For example, it is more preferable to use an enzyme that maintains its activity in a range of 0.101325 MPa (normal pressure) to 7.4 MPa at a temperature of room temperature (298K) to 304K.

(Dispersant)

As the dispersing agent, an emulsifier can be used. Emulsifiers are amphiphilic molecules with hydrophilic groups and hydrophobic groups. As long as it is possible to form a stable molecular aggregate using an emulsifier, the types and combinations of the emulsifiers used in the embodiments are not particularly limited. Emulsifiers include, for example, lipids and lipids, high-spin fatty, fluorescent lipids, cationic surfactants, anionic surfactants, ampholytic surfactants, zwitterionic surfactants, non-ionic surfactants , Polysaccharide surfactants, synthetic polymers, natural polymers such as proteins, and the like can be appropriately selected and used.

For example, N-dodecyl-N, N-dimethyl-3-ammonio-1-propanesulfonate (SB-12) can be used as a bidentate surfactant.

(Molecular aggregate)

In the non-aqueous phase, the nonionic surfactant may be dispersed in the nonionic surfactant by a dispersing agent to form a substantially spherical reversed micelle or a rosaceous micelle on a string or a liposome, a vesicle, a microemulsion, a Rajer emulsion, a continuous microemulsion, a single emulsion in a monodispersed phase, Any one or more molecular aggregates can be formed.

The enzyme body may be obtained by immobilizing an enzyme in such a molecular assembly. For example, as an example of a molecular aggregate, a substantially spherical reversed micelle formed by a dispersant in a non-aqueous phase can hold a predetermined amount of water as a water pool at its center. The enzyme can be immobilized by introducing the enzyme into the water pool of the reverse micelle. Immobilization of the enzyme is also referred to as solubilization of the enzyme in water pool. In enzyme bodies, water pools are used as sites of enzyme reactions catalyzed by enzymes.

The reverse micelle is formed, for example, as follows. When the concentration of the emulsifier reaches the Critical Micelle Concentration (CMC), the hydrophilic and hydrophobic groups of the emulsifier are directed toward the inner and outer sides, respectively, and the nearly inverted micelles surrounding the water .

In addition, the concentration of the emulsifier can be further increased, and the inverted spinel micelles grown in the rosacea can be formed by growing the spherical reverse micelles. The water in the center of the reverse micelle is the reaction field of the enzymatic reaction as the reverse micelle. In addition, by using the reverse-racemic micelle as an enzyme substance, the non-aqueous phase containing the enzyme substance can be gelated. The details of the gelation of the non-aqueous phase will be described later.

In place of the emulsifier, a surfactant such as 1,2-bis (2-ethylhexylcarbonyl) -1-ethanesulfonate (AOT) may be added to a nonaqueous solvent to prepare a reverse micelle and reverse- Can be produced. In the non-aqueous phase, when the concentration of AOT is increased, the reverse roughened micelle can be formed. Further, when the concentration of AOT is continuously increased, the reverse roots micelle is intertwined with each other to gell the entire non-aqueous medium.

As other molecular aggregates, a single emulsion (a W / O monodispersed emulsion (for example, a w / o monodisperse emulsion) formed by a dispersant such as a liposome, a vesicle, a microemulsion, a Razor emulsion, a continuous microemulsion, ), A double emulsion (W / O / W type double emulsion), or a multi-layer emulsion. These molecular aggregates may contain an aqueous phase as an aqueous phase or an aqueous phase as an aqueous water phase.

In addition, the aqueous medium containing the molecular aggregate as an inner water phase or water phase may contain, for example, a polar ion liquid as described above. (IL + W) / O microemulsion (water-in-water emulsion), reverse micelle [(IL + W) / O], or the like, which is formed by mixing a polar ion liquid and a water solvent, (IL + W) of a mixed solvent containing an ionic liquid (IL) such as reversed-phase inverted micelles and a water solvent (W).

Also, in the water pool, water present in the vicinity of the hydrophilic group of the molecule of the dispersant molecule or the protonic ionic liquid (PIL) in the state in which the molecular motion is bound by the ion-dipole interaction is called the binding water. On the other hand, the water present in the center of the water pool is a free water in substantially the same state as the bulk water. Between the free water and the coupling water, the exchange is performed quickly. The free water increases with the increase of the water content ω _o . The water content ω _o is obtained by the following equation.

Here, [H ₂ O] is the molar concentration of water and [S] is the molarity of the dispersant (S).

Further, the radius Rw of the water pool is obtained by the following equation.

When a protonic ionic liquid (PIL) is used as an ionic liquid, PIL also acts as an auxiliary surfactant and contributes to the formation of reverse micelles or a microemulsion (W / IL type). Therefore, it is necessary to consider the amount of PIL used for forming the reversed micelle or microemulsion (W / IL). In general, the water content ω _o becomes larger when the PIL amount is increased in the concentration [S] of the certain surfactant.

By properly adjusting the water content omega _o , the size of the water pool can be appropriately adjusted. However, when a solvent such as a polar ion liquid is present in the water pool in a cavity, the water content? _O may deviate from the above formula.

Molecular aggregates such as the above-mentioned reverse micelle, reverse osmotic micelle, liposome, vesicle, microemulsion, Raser emulsion, W / O monodispersed emulsion or W / O / W type double emulsion can also be coated with a gel or a polymeric material .

A molecular aggregate such as reverse micelle, liposome, vesicle, microemulsion, Raser emulsion, W / O monodispersed emulsion, or W / O / W type double emulsion coated with a gel or polymer can be regarded as a microcapsule have.

In order to improve the stability of the molecular assembly and the efficiency of the enzymatic reaction, it is also possible to use an organic material such as oxide graphene, carbon nanotube, graphene, carbon nanohorn, silica nanoparticles, silver nanoparticles, gold nanoparticles, One or more of the mesoporous materials can be dispersed inside, on the surface, or around the molecular aggregate. Here, the inside of the molecular assembly is, for example, a water pool such as reverse micelle or a center portion of reverse roughened micelle. Among them, when graphene oxide, carbon nanotubes, graphene, carbon nanohorn, silver nanoparticles, gold nanoparticles, and palladium nanoparticles are dispersed, it is possible to obtain high electron conductivity, ionic conductivity, Can be obtained. On the other hand, when silica nanoparticles, semiconductor nanoparticles, and mesoporous materials are dispersed, the stability of the molecular aggregate can be improved.

In addition to the above dispersion, the copper nanoparticles may be dispersed alone or together with at least one of the dispersions. Even when the copper nanoparticles are dispersed, the electronic conductivity and the ion conductivity can be improved, and the stability of the molecular assembly can be improved.

When a pair of electrodes are provided on the non-aqueous electrolyte as described later, care should be taken not to short-circuit the electrodes by these materials. For example, it is possible to prevent shorting of the electrode by dispersing the material inside the molecular aggregate, or by disposing each electrode sufficiently apart. In addition, it is preferable to reduce the size of the material in order to prevent short-circuiting of the electrodes.

(Microcapsules)

The microcapsule according to the embodiment is obtained, for example, by wrapping a core portion including a minute nucleus (solid, liquid, gas) with a porous wall film, and indicates a size ranging from nanoscale to millimeter. The microcapsule in the enzyme body has effects such as prevention of modification of the enzyme, isolation from the non-aqueous solvent, storage and concealment.

The above-mentioned modification of the enzyme includes, for example, denaturation or inactivation of the enzyme.

The core portion of the microcapsule according to the embodiment is used as a site for an enzyme reaction. In addition, the microcapsules can quickly introduce a component relating to an enzyme reaction such as a substrate, a mediator, water, and an intermediate product with the core, and can rapidly release the reaction product of the enzyme reaction from the core.

As the material of the wall film of the microcapsule, that is, the shell portion, a hygroscopic polymer material or other polymer material which can be used, for example, as a carrier can be used. That is, the wall film of the microcapsule may be any one of an organic wall film including a hygroscopic polymer material and a polymer material, an inorganic wall film, and an inorganic / organic hybrid wall film.

Microcapsules can generally be produced by three techniques: chemical techniques, physicochemical techniques, and mechanical and physical techniques. Among these techniques, there are methods such as interfacial polymerization method of chemical technique, in-situ polymerization method, curing coating method in liquid, and in-liquid drying method of physico-chemical technique as a technique of producing microcapsules of spherical mononuclear.

The related microcapsules according to the embodiment can be produced by the above-described method, but also by using, for example, a double emulsion produced by a two-step emulsification method, a film-milk method, or a one-step emulsification method as a template . Particularly, the microcapsules obtained by using the double emulsion produced by the one-step emulsion method as a template have fewer impurities in the core material, less fluctuation in the particle diameter, number of cores, and particle diameter of the core, Since it can be contained in the core portion.

Alternatively, microcapsules may be prepared by photopolymerization of the dispersant using a reversed micelle or vesicle or double emulsion formed by a reactive dispersant.

An enzyme body in which the enzyme is held in the microcapsule can be used. Such enzyme bodies can be obtained, for example, by preparing microcapsules by encapsulating enzymes in the microcapsules to be produced when the microcapsules are prepared by the above-described method. Instead of the enzyme, cells or microorganisms to be described later may be retained in the microcapsules. Before the microcapsule (enzyme body) containing the enzyme thus obtained is dispersed in the non-aqueous medium, it may be immersed in a water solvent to contain water in the core portion or the wall film.

(Cells and microorganisms)

As the enzyme body, cells or microorganisms including an enzyme can be used. Cells and microorganisms can be used as an enzyme body in a single body. Alternatively, a cell or a microorganism immobilized on a carrier binding method or an inclusion method may be used as an enzyme body.

Alternatively, cells or microorganisms may be coated with a gel or a polymer material to form an enzyme body. Details of the gel or polymer material for coating cells or microorganisms will be described later. When cells or microorganisms are coated with gel, extracellular matrix protein (ECM protein) or extracellular matrix (Fibronectin: FN) may be coated together with the gel.

Cells and microorganisms present in nature contain various enzymes, and some have enzymes or combinations of enzymes useful for the immobilization of carbon dioxide or conversion to fuel. By selecting a cell or a microorganism having an appropriate combination of enzymes, it can be used as an enzyme body of the embodiment. The cells usable in the embodiments may be cells other than microorganisms, for example, animal cells or plant cells. Also, instead of the above microorganisms or cells, a biological group, generically referred to as a seaweed, having light such as sunlight or artificial light as an energy source, may be used.

Cells or microorganisms may be used in a killed state without proliferation. The microorganisms in such a dead state are said to be in a static state, and immobilized microorganisms are referred to as immobilized suspended microorganisms.

(Support)

As the supporter for immobilizing the enzyme, for example, chitin on a powdery or porous bead, chitosan (for example, chitopearl BCW3010 made by Fuji Bouchi), xylan, κ-carrageenan and the like can be used. As the support, for example, porous glass, polylactic acid, alumina, silica gel, and celite can be used. In addition, polysaccharide derivatives such as cellulose, dextran, and agarose, for example, can be used as a support.

The shape of the support is not particularly limited and may be a shape other than the above-mentioned powdery form or porous beads. For example, in the case of cellulose, it can be used as a nonwoven fabric in addition to the form of a cellulose powder. As the support, for example, cellulose powder, cellulose nanofiber (CNF), cellulose nano-crystal (CNC), chitin nanofiber, or chitosan nanofiber can be used. A typical CNF has a width of about 4 nm to 100 nm and a length of about 5 탆, and a typical CNC has a width of about 10 nm to 50 nm and a length of about 100 nm to 500 nm. For example, [BiNFi-s], which is a nanofiber derived from cellulose, chitin or chitosan made by Sugino Machine, may be used. Also, &quot; BiNFi-s &quot; has a diameter of about 20 nm and a length of several mu m.

The carrier is modified with an enzyme by a carrier binding method (physical adsorption method, ion-binding method, covalent bonding method), or the enzyme is dispersed on a carrier to prepare a complex. Alternatively, the support is modified with an enzyme by, for example, a lattice-like support by the inclusion method (lattice type), and the enzyme is dispersed in the grid structure of the support to prepare a complex. The thus obtained complex can be used as an enzyme body.

Further, when the enzymes are modified on the lattice-like support by the inclusion method, the enzyme can be trapped in the mesh of the support.

Further, a polymer material can be used as a support. As a polymer material (polymer material) usable as a support, natural polymers or synthetic polymers are used as raw materials.

Starch-acrylic acid graft polymer, starch-styrene sulfonic acid graft polymer, starch-vinyl sulfonic acid graft polymer, starch-acrylamide graft polymer, etc.), cellulose (starch-acrylonitrile graft polymer, (Cellulose-acrylonitrile graft polymer, cellulose-styrene sulfonic acid graft polymer, cross-linked product of carboxymethyl cellulose), other polysaccharide type (hyaluronic acid, agarose), protein type (collagen etc.).

A polymer material having a synthetic polymer as a raw material is excellent in terms of mechanical strength and chemical stability. Examples of the synthetic polymer include polyvinyl alcohol type (polyvinyl alcohol crosslinked polymer, PVA absorbing gel, freezing / thawing elastomer, etc.), acrylic type (crosslinked sodium polyacrylate, sodium acrylate-vinyl alcohol copolymer, polyacrylonitrile (Ethylene glycol-diacrylate crosspolymer, etc.), condensation polymer (ester polymer, amide polymer, etc.), other polymer (maleic anhydride polymer, vinylpyrrolidone copolymer and the like) ) Can be used.

The polymer material may be appropriately processed into various shapes such as powder, bead, fiber, film, and nonwoven fabric depending on the use.

The polymer material is used as a carrier, the carrier is modified with an enzyme by a carrier binding method (physical adsorption method, ion-binding method, covalent bonding method), and the enzyme is dispersed on a carrier to prepare an enzyme body. Alternatively, for example, an enzyme body is prepared by using a lattice-like support, modifying the supporter with an enzyme by the inclusion method (lattice type), or dispersing the enzyme in a grid structure of the supporter.

As a support for immobilizing the enzyme, a polymer gel (polymer gel) may be used. Examples of such gels include, but are not limited to, Metrogel (MeTro Hydrogel), gelatin methacrylate (GelMA) hydrogel, gelatin, alginic acid hydrogel, polyacrylic acid sodium gel, mebel gel (manufactured by Ikeda Chemical Industries, ; Mebiolgel, a room temperature solidified / stretchable hydrogel AQUAJOINT (trade name, manufactured by Nissan Chemical Industries, Ltd.), silica gel, agar, κ-carrageenan, and polyacrylamide gel.

An enzyme body can be prepared by dispersing and modifying an enzyme by the binding method (physical adsorption method, ion-binding method, covalent bonding method), or encompassing the enzyme with gel by the inclusion method.

Method for removing and recovering CO _2, such as a physical absorption separation using absorbent or absorbent, membrane separation process, the CO ₂ compression and sequestration, there are various constraints described below:

(1) Can only be applied to low-pressure gas

(2) Use of corrosion resistant reaction vessel is necessary

(3) Thermal energy is needed

(4) Hydrogen gas needs to be separated

(5) Need energy to separate oxygen

(6) Desulfurization is necessary.

Further, when converting from CO ₂ to fuel such as methanol using an electrochemical conversion method, a large overvoltage is required. In addition, there are problems such as many by-products in the electrochemical method.

On the other hand, the fuel conversion method from CO ₂ using an enzyme does not have the above-mentioned restrictions, and a smaller overvoltage can be used as compared with an inorganic catalyst such as a metal catalyst. Therefore, conversion of CO ₂ into fuel by an enzyme is a suitable conversion method.

[Mediator]

The mediator according to the embodiment is not particularly limited as long as the mediator is a mediator of the enzyme reaction catalyzed by the enzyme. Here, the mediator may act as a reducing agent itself in the enzymatic reaction for reducing the reactant, or may act as a coenzyme in the enzymatic reaction for reducing the reactant.

For example, NADH (nicotinamide adenine dinucleotide) and PQQ (pyrroloquinoline quinone) are coenzymes and can be considered as mediators.

Mediators are needed in many enzymatic reactions that produce fuels from carbon dioxide by enzymatic reactions. When NADH is used as a mediator, NADH serves as a coenzyme.

In addition to the above-nicotinamide adenine dinucleotide (NADH) (reduced form) / nicotinamide adenine dinucleotide (NAD ⁺⁾ (oxidized form), NADPH / NADP ^{+, +} MV / MV ⁺² (methyl viologen), potassium ferricyanide / (3,3 ', 5,5'-tetramethylbenzidine (TMB) / 3,3', 5'-tetramethylbenzidine , 5'-tetramethylbenzidine diimine can be used. In addition to the pyrroloquinoline quinone (PQQ) described above, iodine, p-nitrophenol, phenol, aromatic amine and the like may be used as a mediator.

Another mediator is p-cresol.

The water-soluble mediator can be used, for example, in a water pool of an enzyme body, and can function as a mediator.

NADH participates in many enzyme reactions as coenzymes, which then provide electrons or protons and are oxidized to NAD ⁺ , the oxidative chain. On the other hand, since NADH is very expensive, reuse by reduction from oxidized product NAD ⁺ is demanded. The regeneration method of NADH has already been studied by a chemical method, an electrochemical method, a photoelectrochemical method, an enzyme method and the like. Among them, the method of producing NADH by an electrochemical method is one of the most promising methods because the addition of a reducing reagent is not required and the cost is low.

In the carbon dioxide immobilization apparatus according to the embodiment, when the oxidized mediator is regenerated by an electrochemical method, for example, a cathode electrode and an anode electrode are provided so as to be in contact with the non-aqueous solution. As described later, the mediator can be regenerated by an action (for example, a reduction reaction) by the cathode electrode.

On the other hand, when electrochemical reduction from NAD ⁺ to NADH is carried out using a common electrode, NAD ⁺ is reduced to an enzyme-active NADH (coenzyme) as well as dimer NAD ₂ having no enzyme activity. In addition, since, compared to the reaction NAD ⁺ is reduced to NADH, dimer faster production rate of NAD _2, if the reduction of NAD ⁺ electrochemically, is presented mainly dimers are generated reduced NAD _2. The dimeric NAD ₂ is enzymatically inactive, i.e., it has no function as a coenzyme.

On the other hand, NADH functions as a coenzyme, but its production rate is slower than that of the formation reaction of dimeric NAD ₂ . Therefore, by the production of dimeric NAD ₂ , the amount of NADH capable of participating in the enzyme reaction is gradually reduced.

Therefore, in order to reduce the reduction potential (overvoltage) of NAD ⁺ , it is preferable to use another mediator. That is, in the non-aqueous medium or water in the pool that comprises a NAD ^+, it is possible to disperse the mediator to the reduction of NAD ^+. NAD ⁺ can be reduced by this mediator. As will be described later in detail, the oxidized mediator can be reduced by, for example, the action of the cathode electrode.

When other mediators are used together with NAD ⁺ , other mediators can be used, for example, hydroquinone, ferricyanide, ferrocene, organic pigments, transition metal complexes and the like. These mediators can be dispersed in the non-aqueous medium.

Alternatively, during the non-aqueous phase, a catalyst layer capable of reducing NAD ⁺ at a lower overvoltage may be provided. This catalyst layer can be provided on, for example, a cathode electrode. The catalyst layer can be provided on the electrode by, for example, electrolytic polymerization, direct injection spraying method, coating method, impregnation method, or the like.

For example, an electrolytic film of poly (Neutral red) (abbreviation: Poly (NR)) can be formed on the porous film by electrolytic polymerization. By using a porous membrane with a poly (NR) modified membrane, it is possible to efficiently reduce NAD ⁺ to NADH with enzyme activity at a relatively low overvoltage (-600 mV vs. Ag / AgCl).

On the other hand, when reducing from NAD ⁺ to NADH, not only electrons (e ^- ) but also protons (H ⁺ ) are required. This proton can be supplied, for example, from an aqueous phase as a proton source. Details of the case where the water phase is a proton source will be described later.

In the carbon dioxide immobilization apparatus according to the embodiment, when the mediator in the oxidized state is regenerated by an enzymatic method, that is, by use of an enzymatic reaction, it contains, for example, an enzyme catalyzing a reaction for reducing the oxidant of the mediator Can be used. As a specific example, when NADH / NAD ⁺ is employed as a mediator, an enzyme body containing GDH can be used.

The method for regenerating the mediator is not limited to the method described in detail above, and for example, various chemical methods, electrochemical methods, photoelectrochemical methods, enzyme methods, and the like can be employed. One mediator regeneration method or a plurality of mediator regeneration methods may be employed. For example, an electrochemical method and an enzymatic method may be used in combination.

When only a mediator other than the coenzyme (for example, NADH) is used, for example, ferrocene or the following hydrophobic mediator (decamethylferrocene, 1,2-diferosenylethylene, tetramethyl-p-phenylenediamine) Can be used.

[electrode]

As described above, in the carbon dioxide immobilization apparatus according to the embodiment, when the carbon dioxide is reduced in the enzymatic reaction, or when the reduction product (intermediate product) of carbon dioxide is reduced, Method can be used. When an electrochemical method is adopted for reducing and regenerating the mediator, a pair of electrodes, for example, a cathode and an anode, are provided in the non-aqueous phase. These cathodes and anodes can be contained in, for example, a non-aqueous medium (ion liquid). Further, although a porous electrode may be used for each of the cathode and the anode, in such a case, these electrodes can also function as a porous film.

The cathode electrode serves, for example, to regenerate the coenzyme NADH consumed in the enzymatic reaction of carbon dioxide or to reduce the oxidized mediator. That is, the cathode electrode functions as a cathode. On the other hand, the anode electrode is paired with the cathode electrode and functions as an anode.

As the electrolyte for the non-aqueous electrolyte, for example, a support salt may be added. Examples of support salts include KCl, Tetrabutylammonium perchlorate (TBAP), and the like.

In addition, the ionic liquid contained in the non-aqueous phase may have a function as an electrolyte itself. In that case, it is not necessary to separately add an electrolyte to obtain the action of the electrodes (cathode and anode).

When the cathode electrode and the anode electrode are used as the working electrode and the counter electrode, a three-electrode system can be designed by providing a reference electrode or a pseudo reference electrode in addition to the non-aqueous solution in addition to the cathode electrode and the anode electrode. Alternatively, a four-electrode system can be designed by providing, in addition to the cathode and the anode, two reference electrodes (two in total) or pseudo reference electrodes (two in total) corresponding to the cathode and the anode, respectively. By using the reference electrode or the pseudo reference electrode, the voltage for reducing the mediator can be accurately controlled. Therefore, the mediator can be efficiently reproduced. The reference electrode and the pseudo reference electrode can be provided at any place in the non-aqueous phase, but are preferably provided between the cathode electrode and the anode electrode.

Alternatively, the reference electrode and the pseudo reference electrode may be provided at any place in the water phase. In view of the advantages such as ease of maintenance, it is preferable to provide the reference electrode and the pseudo reference electrode in the water phase. Further, when the reference electrode is provided on the water phase, it is not necessary to use a reference electrode for an organic solvent.

As described above, when the reference electrode and the pseudo reference electrode are properly set in the fuel generating section, the current value and the product concentration (for example, the fuel concentration) are stabilized when the constant current is set. In addition, when the voltage is set to a constant voltage, a stable applied electric potential value can be maintained, and a product (fuel) of high purity can be obtained.

In the case of using the non-porous electrode as the cathode electrode and the anode electrode, the diffusion of the substrate and the intermediate product of the enzyme reaction in the non-aqueous phase and the aqueous phase, the fuel, the coenzyme and other mediators and proton ions It is preferable to provide the cathode electrode and the anode electrode, respectively. On the other hand, when the cathode electrode and the anode electrode can also function as a porous film, the position at which the cathode electrode and the anode electrode are provided is not particularly limited.

For example, the cathode electrode can be provided between the non-aqueous phase and the aqueous phase. Further, for example, the anode electrode can be provided between the gas phase and the non-aqueous phase. Further, for example, by arranging a plurality of cathode electrodes during non-aqueous recording, it is also possible to divide the non-aqueous recording area into a plurality of regions. When the water phase is used as the proton source of the proton used for regenerating the mediator, the proton can be efficiently supplied to the cathode electrode by providing the cathode electrode as a porous film between the non-aqueous phase and the aqueous phase, .

The material of the cathode electrode and the anode electrode may be selected from a conductive material, and the material thereof is not particularly limited. For example, commercially available carbon, carbon cloth, carbon fiber, carbon nonwoven fabric, and carbon paper can be used. In addition, a composite electrode material including a thin piece of graphene or a carbon nanotube can be used. The electrode using these materials can also function as a porous film. In the case where one surface of the electrode that also serves as the porous film is exposed to the atmosphere such as the atmosphere, for example, a gas diffusion layer may be provided on the surface exposed to the gas phase in order to promote the supply of carbon dioxide to the non-aqueous solution. The gas diffusion layer is a microporous layer mainly containing carbon and a water repellent material.

In addition, an electrode of a metal material may be used as a cathode electrode and an anode electrode. For example, electrodes including platinum, gold, and silver may be used. On the other hand, in terms of cost, it is preferable to use a titanium electrode.

As the reference electrode and the pseudo reference electrode, for example, electrodes such as platinum, white gold, palladium, silver, silver / silver chloride (Ag / AgCl) electrode, gold and carbon electrode can be used.

Specific examples of the material of the cathode electrode and the anode electrode include carbon felt, carbon nanofiber nonwoven fabric, foam (graphene foams) (e.g., graphene foams having a continuous three-dimensional network with continuous 3D networks).

Foamed (foam) graphenes can be made, for example, by first forming a graphene layer on a nickel-foam by chemical vapor deposition (CVD) method, and then removing the base of nickel. Since the expanded graphene has many pores, it is possible to penetrate the non-aqueous medium (ion liquid) to the center. Foamed graphenes also have the advantages of being robust, flexible and easy to handle.

The electrode (including the cathode electrode, the anode electrode, the reference electrode, and the pseudo reference electrode) may be formed into a plate shape, a rod shape, a mesh shape, a wire shape, a foam shape, a cloth- form, and the like.

[Porous film]

A porous film may be provided between the gas phase and the non-aqueous phase, or between the non-aqueous phase and the aqueous phase. In addition, the non-aqueous phase can be divided into a plurality of non-aqueous phase by providing the non-aqueous phase with a porous film.

As described above, a porous cathode electrode or an anode electrode may be used as the porous film, but a porous film that is separate from the cathode electrode and the anode electrode may be used. In this case, inorganic or organic materials such as glass, ceramics, polymers and the like can be used as the material of the porous film in addition to the above-described electrode materials.

Further, it can be suitably modified to a water repellent film, a hydrophilic film, a modified film, a metal nano-particle or the like at a proper position on the surface of the porous film. When the cathode electrode and the anode electrode also serve as a porous film, these electrodes may be similarly modified with a water repellent film, a hydrophilic film, a modified film, metal nanoparticles, or the like.

As the modified film, for example, Poly (NR) can be modified by electrolytic polymerization.

Further, when the porous membrane is provided between the water phase, a permeation-separating membrane, a proton exchange membrane (PEM) or a protic ionic liquid membrane may be further provided on the surface of the porous membrane facing the water side.

<Awards>

The carbon dioxide immobilizer according to the embodiment includes an aqueous phase containing an extract containing water.

The extract may contain a buffer. The type and concentration of the buffer solution can be appropriately selected depending on the kind of the reaction system or the mediator. A buffer adjusted appropriately can function as a proton source for regenerating the mediator and regenerating it.

The extraction solution is not particularly limited, and an aqueous solution capable of rapidly extracting the reaction product can be used as the extraction solution. As the extract, it is preferable to use an aqueous solution capable of continuously supplying the proton with the non-aqueous phase.

<Separator>

The carbon dioxide immobilization apparatus according to the embodiment may further include a separator. The portion where the separator is provided can be changed according to the design of the apparatus. For example, a separator may be provided between the non-aqueous phase and the aqueous phase, or a separator may be provided adjacent to the electrode serving also as the porous film. However, the location of the separator is not limited thereto.

The separator is preferably selected from a material capable of selectively transmitting a substrate, a fuel, and a mediator. It is preferable that the separator is selected from an insulating material.

The separator can be a stand-alone type or a composite type material. For example, a composite type separator that is modified with a porous film and integrated with the porous film can be used. Alternatively, a single separator that is not integrated with the porous film can be used.

When the separator is installed, for example, between the gas phase and the non-aqueous phase, the carbon dioxide is selectively permeated and the intermediate product (for example, formic acid or formaldehyde) or the end product (for example, fuel such as methanol) To avoid this, a hydrophobic separator can be used, for example.

On the other hand, when the separator is provided between the non-aqueous phase and the aqueous phase, for example, considering the movement of proton ions from the aqueous phase to the non-aqueous phase and the diffusion and extraction of the fuel from the non- aqueous phase to the aqueous phase, Or a hydrophilic material.

The separator can be selected from a polymer membrane. As the polymer membrane, a homogeneous membrane, a composite membrane, and a polymer membrane including an asymmetric membrane can be selected. In addition, a Nafion (registered trademark) film may be used as a separator. Particularly, it is preferable to use a permeation-separating membrane which selectively passes water and reaction products and ions, and does not pass through enzymes, enzyme bodies, ionic liquids and the like.

The thickness of the separator can be appropriately selected depending on the permeation rate of carbon dioxide in the gas phase, and the permeation rate of ions and molecules in the non-aqueous phase or water phase.

Hereinafter, specific examples of the structure of the carbon dioxide immobilizer according to the embodiment will be described with reference to the drawings. In the embodiments, the same reference numerals are given to common components, and redundant description is omitted. In addition, although each figure is a schematic diagram for explaining the embodiment and promoting the understanding thereof, there is a place different from the actual apparatus in shape, dimension, ratio, etc., .

FIG. 1 shows an example of a carbon dioxide immobilization apparatus for reducing carbon dioxide to an end product through an enzyme reaction in three steps, corresponding to the first embodiment of the embodiment.

The carbon dioxide immobilizer 100 shown in FIG. 1 comprises a first block 110, a second block 120, and a third block 130.

The first block 110 includes a first cell body C1 having a space in which the gas phase 111, the non-aqueous phase 112 and the water phase 113 are accommodated or in which they are accommodated. The second block 120 includes a second cell body C2 having therein a space in which the first water 123a, the non-water 122 and the second water 123b are received or in which they are received . The third block 130 includes a third cell body C3 having a first water receiving chamber 133a, a non-water receiving chamber 132 and a second water receiving chamber 133b, .

Herein, the non-water phase 112 of the first block 110, the non-water phase 122 of the second block 120, and the non-water phase 132 of the third block 130 correspond to the first non- It can be regarded as the non-award and the third non-award.

It is also possible to regard the water surface 113 in the first block 110 and the first water surface 123a at the front end of the second block 120 as the first water surface. The second water column 123b at the rear end of the second block 120 and the first water column 123a at the front end of the third block 130 can be regarded as the second water column. The second water column 133b at the rear end of the third block 130 can be regarded as the third water column.

More specifically, in the first block 110 of the carbon dioxide immobilizer 100, the gas phase 111 containing carbon dioxide, the ionic liquid, the enzyme body 11, the mediator (the reducing body 14a and the oxidant A water phase 113 including a non-aqueous phase 112 containing the first reaction product 15a and a non-aqueous phase reaction product 14b and an extraction liquid for extracting the first reaction product 15 from the non-aqueous phase 112 is accommodated in the first cell body C1 .

In the first block 110, the cathode electrode 115 and the anode electrode 114 for reducing the oxidant 14b of the mediator to the reducing body 14a of the mediator and the anode electrode 114 are brought into contact with the non- Is installed. The first block 110 further includes a cell voltage control unit for controlling a voltage (or a potential) applied to the cathode electrode 115 and the anode electrode 114. [ In the first block 110, the cathode electrode 115 and the anode electrode 114 are electrodes containing a porous material.

The cell voltage control unit may be replaced with a current control unit. The current control unit controls the current flowing between the cathode electrode 115 and the anode electrode 114.

The illustrated electric control unit 151 may be a cell voltage control unit for controlling the voltage applied to the cathode electrode 115 and the anode electrode 114. [ Alternatively, the electric control unit 151 may be a current control unit for controlling a current flowing between the cathode electrode 115 and the anode electrode 114. [ The electric control unit 151 may be provided with a mode functioning as a cell voltage control unit and a mode functioning as a current control unit.

The cathode electrode 115 is, for example, a cathode (cathode), and is provided between the non-aqueous phase 112 and the aqueous phase 113 and also functions as a porous film. The anode electrode 114 is, for example, an anode (anode), and is provided between the gas phase 111 and the non-aqueous phase 112 to function also as a porous film. The cathode electrode 115 and the anode electrode 114 are connected to each other by the inner space of the first cell main body C1 as three chambers, that is, the gas for the gas phase 111, For example. The cathode electrode 115 shown in Fig. 1 is provided between the non-aqueous phase 112 and the aqueous phase 113, but it can be provided at any other place in the non-aqueous phase 112. For example, it is preferable that the cathode electrode 115 be provided in the vicinity of the interface between the non-aqueous phase 112 and the aqueous phase 113 and not in contact with the aqueous phase 113. Likewise, the anode electrode 114 can be provided at any place in the non-aqueous phase. When the anode electrode 114 is provided between the non-aqueous phase 112 and the vapor phase 111, a part of the anode electrode may be exposed in the vapor phase.

In the first block 110 of FIG. 1, a two-electrode system configuration is shown, but a three-electrode system or a four-electrode system configuration may be employed. A reference electrode or a pseudo reference electrode may be provided at an arbitrary place in the non-aqueous electrolyte (112) in addition to the cathode electrode (115) and the anode electrode (114). As described above, by using the reference electrode or the pseudo reference electrode, the voltage for reducing the oxidizer 14b of the mediator can be more accurately controlled, and the mediator can be efficiently regenerated.

In addition, the reference electrode and the pseudo reference electrode may be provided at arbitrary positions in the water phase 113. For example, as a modified example, the reference electrode 116 may be provided in the water phase 113 as in the case of the carbon dioxide immobilizer 101 shown in Fig. 14, the second block and the third block of the carbon dioxide immobilizer 101 are omitted, and only the first block 110 is shown in order to simplify the explanation. Except for the presence or absence of the reference electrode 116, there is no difference between the carbon dioxide immobilizer 100 and the carbon monoxide immobilizer 101, which is a modification thereof, and therefore other details will be omitted.

The enzyme body 11 shown in Fig. 1 is an enzyme body and contains an enzyme 12 therein. The enzyme 12 catalyzes a reaction of reducing carbon dioxide (CO ₂ ) supplied to the non-aqueous phase 112 to the first reaction product 15.

The carbon dioxide contained in the gas phase 111 is selectively absorbed by the ionic liquid contained in the non-aqueous phase 112, so that the carbon dioxide is supplied to the non-aqueous phase 112. By the enzymatic action of the enzyme 12 of the enzyme body 11, the carbon dioxide is reduced to the first reaction product 15. Further, as the carbon dioxide is reduced to the first reaction product 15 by the action of the enzyme 12, the reducing substance 14a of the mediator is oxidized by the oxidizing substance 14b of the mediator. Thereafter, the oxidant 14b of the mediator is reduced by the cathode electrode 115 and regenerated as the reducing body 14a.

Subsequently, the first reaction product 15 thus produced is extracted by the extractant in the water phase 113. The first reaction product 15 is then introduced into the second block 120. Alternatively, for example, if the first reaction product 15 itself, which is an intermediate product, is a useful substance, the first reaction product 15 may be recovered from the water phase 113 and used. When the first reaction product 15 is recovered, an outlet for taking out the recovered product may be formed at a portion adjacent to the water phase 113 of the cell body C1 (not shown).

Flow rate of the gas phase is connected to the gas inlet (CO ₂ inlet) 51 and the gas outlet (CO ₂ outlet port) airflow that is installed on 52, control valve 53 and the gas inlet 51 And can be controlled by a pump (not shown) installed in the gas introduction passage.

In addition, the pressure of the gas phase 111 can be controlled by, for example, controlling the airflow control valve 53 and the pump provided in the gas introduction path. By raising the pressure of the gaseous phase 111, the supply of carbon dioxide to the non-aqueous phase 112 can be promoted.

In the carbon dioxide immobilization apparatus 100 shown in Fig. 1, although the gas phase 111 is accommodated in the first cell body C1, the first cell body C1 may be configured so as not to accommodate the gas phase 111 It can also be adopted. For example, in the carbon dioxide immobilization apparatus 100, the non-aqueous phase (112) may contact the atmosphere directly or through a porous anode electrode (114) or other porous film.

The flow rate of the extract liquid in the water phase 113 is controlled by the liquid flow control valve 57 provided in the liquid extracting inlet 55 and the liquid extracting port 56, Can be controlled by a pump (not shown) provided in the pump 54.

The second block 120 of the carbon dioxide immobilizer 100 includes a first water phase 123a into which the water phase 113 from which the first reaction product 15 is extracted is introduced and an ion liquid, (122a) containing a first reaction product (reducing substance (24a) and an oxidizing substance (24b)) and a second water phase (123b) containing an extracting liquid for extracting the second reaction product (25) from the non- And is accommodated in the second cell main body C2. The ionic liquid contained in the non-aqueous phase 122 of the second block 120 may be the same as or different from the ionic liquid contained in the non-aqueous phase 112 of the first block 110 . The mediators 24a and 24b included in the non-aqueous phase 122 of the second block 120 are connected to the mediators 14a and 14b included in the non-aqueous phase 112 of the first block 110, May be the same as or different from each other.

In the second block 120, the cathode electrode 125 and the anode electrode 124 for reducing the mediator oxidizing body 24b with the mediator reducing body 24a and the anode electrode 124 are brought into contact with the non- Is installed. The second block 120 further includes a cell voltage control unit for controlling a voltage (or a potential) to be applied to the cathode electrode 125 and the anode electrode 124.

The cell voltage control unit may be replaced with a current control unit. The current control unit controls the current flowing between the cathode electrode 125 and the anode electrode 124.

The illustrated electrical control unit 152 may be a cell voltage control unit that controls the voltage applied to the cathode electrode 125 and the anode electrode 124. [ Alternatively, the electric control unit 152 may be a current control unit for controlling the current flowing between the cathode electrode 125 and the anode electrode 124. [ The electric control unit 152 may be provided with a mode functioning as a cell voltage control unit and a mode functioning as a current control unit.

Further, as shown in the figure, in the case of a two-electrode system, the cell voltage control section (electrical control section 152) controls the voltage applied to the electrodes. On the other hand, for example, in the case of a three-electrode system, the cell voltage control unit controls the potential applied to the electrode. In the second block 120, the cathode electrode 125 and the anode electrode 124 are electrodes containing a porous material.

The cathode electrode 125 is, for example, a cathode (cathode), and is disposed between the non-aqueous phase 122 and the second aqueous phase 123b to function also as a porous film. The anode electrode 124 is, for example, an anode (anode), and is disposed between the first water phase 123a and the non-aqueous phase 122 to function as a porous film. The cathode electrode 125 and the anode electrode 124 also serve as a support substrate for the non-aqueous phase (122). The cathode electrode 125 and the anode electrode 124 are formed so that the inner space of the second cell body C2 is divided into three chambers, that is, a chamber for the first water column 123a, And is partitioned into a chamber for two water bodies 123b. The cathode electrode 125 and the anode electrode 124 shown in Fig. 1 are disposed between the first water 123a and the non-water 122 and between the second water 123b and the non- The cathode electrode 125 and the anode electrode 124 can be provided at any other positions in the non-aqueous phase 122. [ For example, it is preferable that the cathode electrode 125 is provided in the vicinity of the interface between the non-aqueous phase 122 and the second aqueous phase 123b and not in contact with the aqueous phase. Similarly, the anode electrode 124 can be provided at any place in the non-aqueous phase 122. For example, it is preferable to dispose the anode electrode 124 in the vicinity of the interface between the non-aqueous phase 122 and the first aqueous phase 123a and not to contact the aqueous phase.

When an extract containing the first reaction product 15 is introduced into the first water phase 123a of the second block 120 from the water phase 113 of the first block 110, The first reaction product 15 is selectively extracted by the liquid or the enzyme body 21 so that the first reaction product 15 is supplied to the non-aqueous phase 122. The first reaction product 15 is reduced to the second reaction product 25 by the enzymatic action of the enzyme 22 of the enzyme body 21. In addition, as the first reaction product 15 is reduced to the second reaction product 25 by the action of the enzyme 22, the reducing agent 24a of the mediator is oxidized by the oxidizing agent 24b of the mediator do. Thereafter, the oxidant 24b of the mediator is reduced by the cathode electrode 125 and regenerated as the reducing body 24a.

Then, the generated second reaction product 25 is extracted by the extractant in the second water phase 123b. The second reaction product 25 is then introduced into the third block 130. Alternatively, if the second reaction product 25 itself, which is an intermediate product, is a useful substance, the second reaction product 25 may be recovered from the second water phase 123b as it is. When the second reaction product 25 is recovered, an outlet for taking out the recovered product may be formed at a portion adjacent to the second water phase 123b of the cell body C2 (not shown) .

The flow rate of the extraction liquid in the first water column 123a and the second water column 123b of the second block 120 is the same as the flow rate of the liquid flow control valve 57, (Not shown) provided in the external flow path 54 connected to the main flow path 55.

The third block 130 of the carbon dioxide immobilizer 100 includes a first water column 133a through which the second water column 123b of the second block 120 from which the second reaction product 25 is extracted is introduced, (132) containing an enzyme body (31), a mediator (a reducing body (34a) and an oxidizing body (34b)) and an extracting liquid for extracting the third reaction product (35) from the non- And the second water column 133b is accommodated in the third cell main body C3. The ionic liquid contained in the non-aqueous phase 132 of the third block 130 is also mixed with the ionic liquid contained in the non-aqueous phase 112 of the first block 110 and the non- The ionic liquid may be the same as or different from the ionic liquid contained in the ionic liquid 122. The mediators 34a and 34b included in the non-aqueous phase 132 of the third block 130 are connected to the mediators 14a and 14b included in the non-aqueous phase 112 of the first block 110, And the mediators 24a and 24b included in the non-aqueous phase 122 of the second block 120 may be the same or different.

In the third block 130, the cathode electrode 135 and its anode electrode 134 for reducing the oxidant 34b of the mediator to the reducing body 34a of the mediator and the anode electrode 134 are brought into contact with the non- Is installed. The third block 130 further includes a cell voltage control unit for controlling a voltage (or potential) applied to the cathode electrode 135 and the anode electrode 134. [ In the third block 130, the cathode electrode 135 and the anode electrode 134 are electrodes containing a porous material.

The cell voltage control unit may be replaced with a current control unit. The current control unit controls the current flowing between the cathode electrode 135 and the anode electrode 134. [

The illustrated electric control unit 153 may be a cell voltage control unit that controls the voltage applied to the cathode electrode 135 and the anode electrode 134. [ Alternatively, the electric control unit 153 may be a current control unit for controlling the current flowing between the cathode electrode 135 and the anode electrode 134. [ The electric control unit 153 may be provided with a mode functioning as a cell voltage control unit and a mode functioning as a current control unit.

The cathode electrode 135 is, for example, a cathode (cathode), and is provided between the non-aqueous phase 132 and the second aqueous phase 133b to function also as a porous film. The anode electrode 134 is, for example, an anode (anode), and is provided between the first water layer 133a and the non-water layer 132 to function also as a porous film. The cathode electrode 135 and the anode electrode 134 also serve as a support substrate for the non-aqueous phase 132. The cathode electrode 135 and the anode electrode 134 are formed so that the inner space of the third cell main body C3 is divided into three chambers, that is, a chamber for the first water column 133a, 2 chamber 133b. The cathode electrode 135 and the anode electrode 134 shown in Fig. 1 are disposed between the first water column 133a and the non-water column 132 and between the second water column 133b and the non- The cathode electrode 135 and the anode electrode 134 can be provided at any other positions in the non-aqueous phase. The cathode electrode 135 and the anode electrode 134 in the third block are formed in the same manner as the cathode electrode 125 and the anode electrode 124 in the second block, .

When the extract containing the second reaction product 25 is introduced into the first water column 133a of the third block 130 from the second water column 123b of the second block 120, The second reaction product 25 is selectively absorbed by the ionic liquid that is supplied to the non-aqueous phase. The second reaction product 25 is reduced to the third reaction product 35 by the enzymatic action of the enzyme 32 of the enzyme body 31. Further, as the second reaction product 25 is reduced to the third reaction product 35 by the action of the enzyme 32, the reducing agent 34a of the mediator is oxidized to the oxidizing agent 34b of the mediator do. Thereafter, the oxidant 34b of the mediator is reduced by the cathode electrode 135 and regenerated as the reducing body 34a.

Then, the generated third reaction product 35 is extracted by the extraction liquid in the second water phase 133b. Thereafter, the third reaction product 35 is recovered as a final product. For example, the third reaction product 35 as the final product can be recovered from the extracting outlet 56.

As shown in the drawing, the extracted liquid derived from the second water column 133b of the third block 130 may be introduced again to the water column 113 of the first block 110 through the external flow channel 54 . At this time, the third reaction product 35 may be concentrated and recovered by providing an apparatus (not shown) for concentrating the third reaction product 35, for example, in the external flow path 54. The pH of the extract can also be adjusted appropriately by connecting a pH adjustment line (not shown) to the external flow path 54 through which the extract is flown.

The flow rate of the extracted liquid in the first water column 133a and the second water column 133b of the third block 130 is the same as the flow rate of the liquid flow control valve (not shown) in the first block 110 and the second block 120, 57) provided in the outer flow path 54 and the pump (not shown) provided in the outer flow path 54 connected to the extraction liquid introduction port 55.

In the carbon dioxide immobilizer 100 shown in FIG. 1, each of the first block 110, the second block 120, and the third block 130 has a cell voltage (or a voltage) The voltage (or potential) relating to both the first block 110, the second block 120, and the third block 130 is unified and controlled by the control unit (electrical control units 151, 152, and 153) One cell voltage control unit may be used.

Even if the electric control unit functions as a current control unit, a single current control unit (electric control unit) for uniformly controlling the currents related to the first block 110, the second block 120 and the third block 130 Can be used.

2 is a schematic view of another carbon dioxide immobilizer according to the first embodiment of the present invention.

The carbon dioxide immobilizer 200 shown in FIG. 2 includes a first block 210, a second block 220, and a third block 230 in the same manner as the carbon dioxide immobilizer 100 of FIG. 1 . 1, the first block 210 of the carbon dioxide immobilizer 200 includes a vapor phase 211, a non-aqueous phase 212, and a water phase 213. The second block 220 includes a non-aqueous phase 222 and a water phase 223 and the third block 230 includes a non-aqueous phase 232 and a water phase 233.

2, the first block 210, the second block 220, and the third block 230 are accommodated in a single cell body C10.

Herein, the non-water phase 212 of the first block 210, the non-water phase 222 of the second block 220, and the non-water phase 232 of the third block 230 correspond to the first non- It can be regarded as the non-award and the third non-award. The water phase 213 of the first block 210, the water phase 223 of the second block 220 and the water phase 233 of the third block 230 are referred to as a first water phase, .

In the case of the carbon dioxide immobilization apparatus 200, as shown in FIG. 2, the water phase 213 of the first block 210 is also in contact with the non-aqueous phase 222 of the second block 220. The extraction liquid contained in the water phase 213 of the first block 210 is extracted after the first reaction product 15 generated in the non-aqueous phase 212 of the first block is extracted, The first reaction product 15 is directly supplied to the reaction chamber 222 to become a substrate for the enzyme reaction in the non-aqueous phase 222. Likewise, the water phase 223 of the second block 220 is in contact with the non-water phase 232 of the third block 230 as well. The extraction liquid contained in the water phase 223 of the second block 220 is extracted after the second reaction product 25 generated in the non-aqueous phase 222 of the second block is extracted, The second reaction product 25 is directly supplied to the reaction chamber 232 to become a substrate for the enzyme reaction in the non-aqueous phase 232.

The structure of the carbon dioxide immobilization apparatus 200 of FIG. 2 can produce the third reaction product 35 as a final product by a multi-stage enzyme reaction with a higher production efficiency with a more compact design.

2, the flow rate control method of the gaseous phase 211 and the recovery method and the pH adjustment method of the final product (third reaction product) from the water phase 233 of the third block 230 are the same as those in Fig. 1 Do. The flow rate of the extract liquid is controlled by the liquid flow control valve 57 provided in the liquid extracting inlet 55.

A cathode electrode 215 and its anode electrode 214 for regenerating the mediator consumed by the enzyme reaction are provided so as to contact the non-aqueous phase 212. A cathode electrode 225 and an anode electrode 224 are provided so as to contact the non-aqueous solution 222 in the same manner. A cathode electrode 235 and its anode electrode 234 are provided so as to be in contact with the non-aqueous solution 232. Each of the cathode electrodes 215, 225 and 235 which are the cathodes and the anode electrodes 224 and 234 which are the cathodes except for the anode electrode 214 in the non-aqueous phase 212, (212, 222, 232) so as to separate the non-aqueous phase and the aqueous phase. The anode electrode 214, which is an anode, is provided between the non-aqueous phase 212 and the vapor phase 211.

The method of installing the cathode electrodes 215, 225, and 235 in the respective non-aqueous phase chambers 212, 222, and 232 shown in FIG. 2 is the same as that of FIG. In the case of the carbon dioxide immobilizer 200 shown in FIG. 2, as shown in the figure, for all the blocks (the first block 210, the second block 220, and the third block 230) The voltage (or potential) to be applied can be controlled by being unified by one cell voltage control section (electrical control section 250). Alternatively, as shown in Fig. 1, the voltage (or potential) may be separately controlled by the cell voltage control unit provided in each block.

Naturally, when the electric control unit 250 functions as a current control unit, one current control unit (electric control unit) may unify the current flowing between the cathode electrode and the anode electrode for all the blocks. Alternatively, a current control unit (electric control unit) may be provided for each block, and the current in each block may be separately controlled.

3 is a schematic view of an example carbon dioxide immobilizer according to the second embodiment of the present invention.

3, the carbon dioxide immobilization apparatus 300 according to the second embodiment of the present invention includes a vapor phase 311, a first non-aqueous phase 312, a second non-aqueous phase 322, A third non-aqueous phase (332), and a single cell body (C10) accommodating the water phase (333). The first non-aqueous phase (312) and the second non-aqueous phase (322) are partitioned by an electrode (315) that also serves as a porous film. The second non-aqueous phase 322 and the third non-aqueous phase 332 are partitioned by an electrode 325 serving also as a porous film.

In order to efficiently proceed the production of the intermediate product and the final product in each step in the multistage enzyme reaction, depending on the activity of the enzymes (12, 22, 32) dispersed in each non-aqueous phase and the catalytic efficiency, The concentration of the enzyme bodies 11, 21, and 31 dispersed in the volume or the non-aqueous phase can be appropriately adjusted.

In the carbon dioxide immobilization apparatus 300 shown in Fig. 3, as in the case of the first embodiment of the carbon dioxide immobilizing apparatuses 100 and 200 shown in Figs. 1 and 2, in the non-water basins 312, 322 and 332, The mediators consumed by the electrodes 315, 325, and 335 are reduced and regenerated by the electrodes 315, 325, and 335 provided in the non-aqueous phase.

In the carbon dioxide immobilization apparatus 300, when the electrode 315 operates as a cathode, the electrode 314 functions as an anode. For the electrode 325 acting as the cathode, the electrode 315 becomes the anode. Further, the electrode 325 becomes an anode with respect to the electrode 335 acting as a cathode.

The application of the potential (voltage) to the electrode pairs can be performed sequentially from the left side to the right side. In other words, first, a potential (voltage) for a predetermined time is applied between the electrode 315 functioning as a cathode and the electrode 314 serving as an anode to reduce the oxidized mediator. Thereafter, a potential for a predetermined time is applied between the electrode 325 as a cathode and the electrode 315 as an anode. Subsequently, a potential for a predetermined time is applied between the electrode 335 as a cathode and the electrode 325 as an anode.

As described above, the potential (or voltage) can be applied intermittently and sequentially to the pair of electrodes 314, 315, 325, and 335 a plurality of times. In this case, the electrode serving as the cathode electrode when applying the potential (or voltage) in one turn can act as the anode electrode when applying the potential (or voltage) in another turn. In the above example, the application of the potential (or voltage) is sequentially performed from left to right. However, the order of applying the potential (or voltage) to the electrode pairs is not limited to this order. For example, the order of application may be controlled depending on the progress of the enzyme reaction in each non-aqueous phase.

As described above, when the potential (voltage) is applied to each pair of electrodes, the potential is applied intermittently and sequentially with a time difference, whereby the oxidized form of the mediator in each non-aqueous phase is reduced The enzyme reaction can be maintained by regeneration.

As shown in Fig. 3, the application of the potential (voltage) to each pair of electrodes can be performed, for example, by switching the switches. Further, the electrodes of each pair of electrodes may be electrically connected to the cell voltage control unit (electrical control unit) through an independent electric circuit (not shown). In this case, a potential (voltage) can be applied to each electrode pair with a predetermined time difference by automatic control using the cell voltage control unit.

In the case of using the current control unit, for example, by switching on and off the switch, a current can flow between the electrode pairs or the current can be cut off. In addition, the electrodes of each pair of electrodes may be electrically connected to the current control unit through an independent electric circuit. In this case, a current can be made to flow with a predetermined time difference between the electrode pairs by automatic control using the current control unit.

In addition, a pair of electrodes, that is, two electrodes, may be used. As a specific example, in the case of the carbon dioxide immobilization apparatus 300, it is possible to omit the installation of two electrodes among the electrodes 314, 315, 325 and 335 shown in Fig. For example, the electrode 315 and the electrode 325 are omitted, and only the electrode 314 and the electrode 335 are provided. Alternatively, the electrode 314 and the electrode 325 are omitted, and only the electrode 315 and the electrode 335 are provided. There is a pair of electrodes, that is, two or more electrodes, and the number of electrodes to be provided in the apparatus is not particularly limited.

When the electrode provided at the interface of each non-aqueous phase is omitted, the other non-aqueous phase comes into direct contact with each other. In the case of omitting the electrode serving also as the porous film, for example, a separator may be provided between other non-aqueous electrolytes. In order to promote diffusion of molecules or ions such as reaction products and mediators, the provision of a porous film such as a separator may be omitted.

When a gas containing carbon dioxide is introduced into the gas phase 311, carbon dioxide is selectively supplied to the first non-aqueous phase 312 by the action of the ionic liquid contained in the first non-aqueous phase 312. By the enzymatic action of the enzyme 12 of the enzyme body 11, the carbon dioxide is reduced to the first reaction product 15.

The resulting first reaction product 15 is further diffused into the second non-aqueous phase 322 and reduced to the second reaction product 25 by the enzyme 22 of the enzyme body 21. The resultant second reaction product 25 is further diffused in the third non-aqueous phase 332 and reduced to the third reaction product 35 by the enzyme 32 of the enzyme body 31.

The resulting third reaction product 35 is then extracted by the extractant in the water phase 333. Thereafter, the third reaction product 35 is recovered as a final product. For example, the third reaction product 35 as the final product can be recovered from the extracting outlet 56.

Further, as shown in the drawing, the extract liquid containing the third reaction product may be led out from the water phase 333, and then may be introduced again from the inlet port of the water phase 333 through the external flow path 54. At this time, by providing an apparatus (not shown) for concentrating the third reaction product 35, for example, in the external flow path 54, the third reaction product can be concentrated and recovered. The pH of the extract can also be adjusted appropriately by connecting a pH adjustment line (not shown) to the external flow path 54 through which the extract is flown.

1 and 2) of the first embodiment of the present invention, the flow rate of the gas phase is controlled by controlling the gas inlet (CO ₂ inlet) 51 and the gas outlet (CO ₂ (Not shown) provided in the gas introduction passage connected to the gas flow control valve 53 or the gas introduction port 51 provided in the gas introduction port 52, 1, even if the gas phase 311 is not accommodated in the cell body C10 but the first non-aqueous phase 312 is exposed to the atmosphere, for example, do.

The flow rate of the extract liquid in the water phase 333 is also controlled by the liquid flow control valve 57 provided in the extract liquid inlet 55 and the liquid outlet 56, (Not shown) provided in the external oil passage 54 connected to the oil passages 55, 55.

Fig. 4 shows a schematic view of a carbon dioxide immobilization apparatus according to another example of the second embodiment according to the embodiment.

The basic constitution of the carbon dioxide immobilizer 400 shown in Fig. 4 is the same as that of the carbon dioxide immobilizer 300 of Fig. 3, but in the case of Fig. 4, the first nonwaterwater 412 The second non-aqueous phase 422 and the third non-aqueous phase 432, as well as the fourth non-aqueous phase 402 containing no enzyme substance. The first non-aqueous phase 412, the second non-aqueous phase 422, and the third non-aqueous phase 432, which are not shown in the drawings for simplicity of explanation, . Although not shown in the drawing for simplicity of explanation, the electric control unit (cell voltage control unit and / or current control unit) is electrically connected to each of the electrodes 415, 425, 435, and 414 shown in the figure.

The fourth non-aqueous phase (402) provided at the front end of the first non-aqueous phase (412) may contain an ionic liquid exhibiting an action of absorbing and concentrating carbon dioxide from the gaseous phase (411). By providing the fourth non-aqueous phase (402), carbon dioxide can be stably supplied to the first non-aqueous phase (412) containing the enzyme body.

The ionic liquid in the fourth non-aqueous phase 402 may be gelled to render the fourth non-aqueous phase 402 as a non-aqueous phase, for example, on the surface of the electrode 414. [ By doing so, the contact area between the vapor phase 411 and the fourth non-aqueous phase can be increased, and the efficiency of absorption of carbon dioxide by the fourth non-aqueous phase 402 can be improved. On the other hand, in the case where the ionic liquid contained in the fourth non-aqueous phase 402 is made into a non-aqueous phase without being gelled, a porous film, for example, is provided between the gas phase 411 and the fourth non- The gas phase 411 and the fourth non-aqueous phase 402 can be partitioned. Alternatively, the gas phase 411 may not be accommodated in the cell body C10.

The separator 441 may be provided adjacent to the electrode 414 provided between the first non-aqueous solution 412 and the fourth non aqueous solution 402 as shown in the figure. As the separator 441, it is preferable to use one capable of selectively transmitting carbon dioxide.

The electrode 414 and the separator 441 may not be adjacent to each other. 5, the separator 441 may be provided between the first non-aqueous phase 412 and the fourth non-aqueous phase 402 and the electrode 414 may be disposed between the vapor phase 411 and the fourth non- Non-aqueous phase (402).

In addition, the electrode 414 can be provided at an arbitrary place in the fourth non-aqueous phase 402. For example, as shown in Fig. 6, the electrode 414 may be provided in the fourth non-aqueous phase 402 so as to follow the external member of the cell body C10. Further, depending on the configuration of the electrode 414, for example, a lead wire 416 as shown in the figure may be used in order to ensure electrical connection with the electrode 414. The electrode 414 may be provided at an arbitrary place in the first non-aqueous solution 412.

4, 5 and 6, a separator 442 may be provided between the third non-aqueous phase 432 and the aqueous phase 433. As the separator 442, it is preferable to use one capable of selectively passing the end product (third reaction product) of the multi-step reduction reaction of carbon dioxide. In the case where the water phase 433 contains a proton source for supplying protons to be used for regenerating the mediator, the separator 442 is preferably one capable of permeating protons.

Also, in the carbon dioxide immobilizer 400 shown in Figs. 4, 5 and 6, since the configuration of a plurality of non-aqueous phase and the arrangement of the electrodes are similar to those of the carbon dioxide immobilizer 300 shown in Fig. 3, As the method of applying the potential (voltage) to the anode, the same conditions and procedures as those in Fig. 3 can be used.

Fig. 7 shows a schematic view of another carbon dioxide immobilizer according to the second embodiment of the present invention.

The carbon dioxide immobilization apparatus 500 shown in Fig. 7 includes a gas phase 511, a first non-aqueous phase 512, a second non-aqueous phase 522, A third non-aqueous phase (532), and a water phase (533).

As shown in the drawing, the gas phase 511 flows into a gas flow channel constituted by the outer cylinder 551 and the intermediate cylinder 552. Each of the first non-aqueous phase (512), the second non-aqueous phase (522), and the third non-aqueous phase (532) has a cylindrical shape. These cylindrical non-aqueous phases are housed so as to be aligned in a direction perpendicular to the center axis (not shown) of the cylinder, that is, in the radial direction of the cylinder. Specifically, the first non-aqueous phase (512) is provided on the outermost side of the cylindrical shape. The third non-aqueous phase (532) is provided on the innermost side of the cylindrical shape. The second non-aqueous phase (522) is provided between the first non-aqueous phase (512) and the third non-aqueous phase (532). The water phase 533 flows into the inner cylinder 553 as a liquid flow path.

The outer cylinder 551 itself may have permeability to a gas containing carbon dioxide or may not have permeability to a gas. It is preferable to provide a gas inlet or the like for introducing a gas containing carbon dioxide between the outer cylinder 551 and the intermediate cylinder 552 when the outer cylinder 551 does not have permeability to the gas.

As the intermediate cylinder 552 and the inner cylinder 553, for example, a cylinder obtained by using a material of a porous film such as a separator can be used.

As the intermediate cylinder 552, it is preferable to use one having permeability to carbon dioxide. As the inner cylinder 553, it is preferable to use a cylinder having permeability to the reduction product of carbon dioxide. For example, a permeation-separation membrane can be used.

7, although the first non-aqueous phase 512 and the vapor phase 511 are in contact through the intermediate cylinder 552, the intermediate cylinder 552 may be omitted. 7, the third non-aqueous phase (532) and the aqueous phase (533) are in contact with each other through the inner cylinder (553). However, the inner cylinder (553) may be omitted.

4, one or more enzymes included in each of the first non-aqueous phase 512, the second non-aqueous phase 522, and the third non-aqueous phase 532, Enzyme bodies and one or more mediators are omitted from the drawings.

In the carbon dioxide immobilization apparatus 500 of FIG. 7, one or more pairs of electrodes 515, 525, 535, and 545 may be provided. In the case where one or more pairs of electrodes are provided, an insulating separator can be provided between the electrodes (not shown) in the same manner as in the method shown in Fig. 3, so that the electrodes are not electrically shorted to each other. In addition, when the non-aqueous phase is thick and there is no possibility of electrical short-circuiting due to contact between the electrodes, a separator may not be provided.

When one or more pairs of electrodes are provided, a method of applying a potential (voltage) to the cathode electrode can follow the application method shown in Fig. 3 (not shown).

Although not shown in the figure for the sake of simplicity of explanation, the electric control unit (the cell voltage control unit and / or the current control unit) is electrically connected to each of the illustrated electrodes.

The carbon dioxide immobilization apparatus 500 is provided with a vapor phase 511 along the center axis (not shown) of the outer cylinder 551 and the intermediate cylinder 552 in the gas flow path including the outer cylinder 551 and the intermediate cylinder 552, (A gas containing carbon dioxide) is distributed. In addition, in the inner cylinder 553 as the liquid passage, the water phase 533 (extract liquid) flows along the central axis (not shown) of the inner cylinder 553.

7 shows a configuration in which the flow path outside the non-aqueous phase is a gas phase and the flow path inside the non-aqueous phase is a water phase. However, for example, Of the flow path can be regarded as a prize.

The carbon monoxide immobilization apparatus 500 is provided with the channel 533 through which the water phase 533 flows and the water phase 533 in the direction perpendicular to the flow direction of the water phase 533 Are adjacent. The carbon dioxide immobilization apparatus 500 is provided with a flow path (an outer cylinder 551 and an intermediate cylinder 552) through which a gaseous phase 511 flows and a non-gaseous phase is formed in a direction perpendicular to the flow direction of the gaseous phase 511 And is adjacent to the vapor phase 511.

The interface between the water phase 533 and the non-water phase can be formed along the length of the flow path through which the water phase 533 flows, so that the contact area between the water phase 533 and the non-aqueous phase can be increased. Therefore, the efficiency of supplying the final product to the water phase 533 can be improved and the recovery rate can be increased.

In addition, since the interface between the gas phase 511 and the non-aqueous phase can be formed along the length of the flow path through which the gas phase 511 flows, the contact area between the gas phase 511 and the non-aqueous phase can be increased. Therefore, the efficiency of supplying carbon dioxide to the non-aqueous phase can be improved.

By using a carbon dioxide immobilization apparatus having a cylindrical water phase 533, non-water phase 512, 522, 532 and a gas phase 511 as shown in Fig. 7, for example, by a multistage enzyme reaction represented by the following formula from a carbon dioxide (CO ₂₎ it can produce methanol (CH ₃ OH).

Each of the reaction steps of the three-step enzyme reaction for producing methanol from left to right in the above formula is composed of a first non-aqueous phase (512) disposed at the outermost one of the non-aqueous phase shown in FIG. 7, And the third non-aqueous phase (532) disposed on the innermost side in the non-aqueous phase.

An electrode that also serves as a porous film sandwiched between the respective non-aqueous phases is operated as a cathode or a working electrode, whereby the NAD ⁺ consumed in the enzyme reaction is simultaneously regenerated. In order to efficiently promote the production of fuel by the multistage enzymatic reaction, it is preferable to adjust the volume of each non-aqueous phase and the amount of the enzyme dispersed in the non-aqueous phase depending on the activity of the enzyme dispersed in each non- The concentration can be appropriately adjusted. For example, the method shown in FIG. 3 can be applied to the method of applying the voltage (or the potential) to the cathode electrode (or the working electrode).

In the first non-aqueous phase (512), the first reaction product (formic acid: HCOOH) produced by the first enzyme reaction using carbon dioxide as a substrate diffuses into the second non-aqueous phase (522) 2 enzyme substrate. Similarly, in the second non-aqueous phase 522, the second reaction product (formaldehyde: HCHO) produced by the second enzymatic reaction using the first reaction product as a substrate is formed in the first non- Is diffused into the third non-aqueous phase (532) and becomes the substrate of the third enzyme reaction. In the third non-aqueous phase (532), the third reaction product (methanol: CH ₃ OH) generated by the third enzyme reaction using the second reaction product as a substrate, that is, the final product, And extracted and recovered by an extract (water phase 533).

Fig. 8 is a schematic view of another carbon dioxide immobilizer according to the second embodiment of the present invention. Figs. 9A, 9B, and 9C show examples of the non-aqueous phase during manufacture of the device.

The carbon dioxide immobilization apparatus 600 shown in Fig. 8 is composed of a gas phase 611, a non-aqueous upper portion 601, and a water phase 633.

The gas phase 611 flows in the gas flow channel defined by the outer cylinder 651 and the intermediate cylinder 652. [ Alternatively, the intermediate cylinder 652 may be omitted. In this case, the gas passage is defined by the outer cylinder 651 and the non-water upper portion 601.

The non-aqueous portion 601 includes a first non-aqueous phase 612, a second non-aqueous phase 622, a third non-aqueous phase 632, an electrode 614, and an electrode 615. The non-aqueous phase portion 601 has a plurality of turns so that a plurality of layered portions are radially arranged, and the first non-aqueous phase 612, the second non-aqueous phase 622, and the third non- Are respectively disposed on the upper portions of the plurality of layers. Further, the inside of the intermediate cylinder 652 can be filled with a nonaqueous solvent such as, for example, an ionic liquid.

In addition, the central portion of the non-water upper portion 601, that is, the space around the winding shaft can be used as a flow path. The water phase 633 flows in the flow path constituted by the non-water upper portion 601 of the thus wound form. Alternatively, as shown in the drawing, the inner cylinder 653 may be provided as the flow path of the water phase 633.

As can be seen from the state during the production of the non-aqueous upper portion 601 shown in FIGS. 9A to 9C, specifically the state before the winding, the non-aqueous upper portion 601 is provided with the separator 641 And a separator 642. The separator 641 is provided between the electrode 615 and the electrode 614. 9A and 9C, the separator 641 is in contact with the surface of the electrode 614, which is opposed to the electrode 615. 9B, the separator 641 is in contact with both of the electrode 614 and the electrode 615. In addition, The position at which the separator 641 is provided is between the electrode 615 and the electrode 614, and is not limited to the illustrated position. For example, the separator 641 may be in contact with the surface of the electrode 615 (the surface facing the electrode 614). The electrode 615 and the electrode 614 are both porous electrodes.

The non-aqueous upper portion 601 includes another separator 642 so that the electrode 615 and the electrode 614 are not in contact with each other after winding. That is, in the non-aqueous upper portion 601 after the winding, the respective members except the non-aqueous solution, that is, the electrode 614, the separator 641, the electrode 615, and the separator 642 are arranged in this order. It is sufficient that the separator 641 and the separator 642 are disposed alternately between the electrode 614 and the electrode 615 in the non-aqueous upper portion 601 after the winding, and the position where the separator 642 is provided is Location. 9A to 9C, the separator 642 is provided so as to be in contact with the electrode 615, but by providing the separator 642 on the right side (right side in each drawing) of the electrode 614, the separator 642 And the electrode 614 may be positioned between the separator 642 and the separator 642. [ Note that the separator 641 and the separator 642 are not shown in Fig.

9A to 9C, the width of the electrode 615 and the electrode 614 (length of the helical shape after winding) may be the same.

9A to 9C, the first non-aqueous phase 612, the second non-aqueous phase 622, and the third non-aqueous phase 632 are formed in the non-aqueous phase portion 601 before being wound, In the direction in which they are wound. Each of these non-aqueous electrolytic capacitors is manufactured by stacking, on a laminate of a porous film obtained by laminating an electrode 614 and a separator 641, for example, in the case of manufacturing the non-aqueous upper portion 601 having the constitution shown in Fig. (Ion liquid, enzyme body, mediator) can be provided by a spraying method, a coating method, a depressurizing method, a casting method, an impregnation method, or the like. The electrode 615 and the separator 642 are sequentially laminated on the respective non-aqueous phase electrodes provided on the electrode 614 to obtain the non-aqueous portion 601 configured as shown in FIG. 9A. Further, each of the non-aqueous phase can be gelated or cured, for example, by the method described below, if necessary.

Alternatively, for example, in the case of manufacturing the non-aqueous upper portion 601 having the constitution shown in FIG. 9B, a laminate of a porous film in which an electrode 614, a separator 641, an electrode 615 and a separator 642 are laminated The material of each non-aqueous phase can be provided on the sieve by the above-described method.

Alternatively, the first non-aqueous phase 612, the second non-aqueous phase 622 and the third non-aqueous phase 632 may be formed by stacking the electrode 614, the separator 641, the electrode 615 and the separator 642, Or may be impregnated in the thickness direction of the laminate. In this case, for example, the material of each non-aqueous phase can be provided on each of the electrode 614, the separator 641, the separator 642 and the electrode 615 before lamination. 9A to 9C, when the multilayer body is wound after the respective non-aquifers are provided on the laminate body or between the layers, the pressure of the winding is appropriately controlled, whereby the non-aqueous phase is separated from the separator 641, The electrode 642, and the electrode 615, respectively.

The first non-aqueous phase 612, the second non-aqueous phase 622 and the third non-aqueous phase 632 are formed in such a manner that a part of each of the first non-aqueous phase 612, the second non- aqueous phase 622 and the third non- (642), and a part thereof may constitute a layer provided on the surface of the porous film. That is, in the non-aqueous portion 601, as shown in FIGS. 9A to 9C, a part of each non-aqueous phase is present on the surface of the porous film or between the porous films and the other portion is impregnated into the porous film . For example, in the case of the configuration of Fig. 9C, for each of the first non-aqueous phase 612, the second non-aqueous phase 622 and the third non-aqueous phase 632, between the separator 641 and the electrode 615 A portion existing on the surface of the separator 642 and a portion impregnated in the electrodes 614 and 615 and the separators 641 and 642 may exist.

As described above, when the non-aqueous phase is gelated or cured, for example, in addition to the enzyme substance and the mediator, a gelling agent or a polymer material, a binder, a crosslinking agent, a carrier, etc. are previously mixed . Thus, by laminating the electrode 614, the separator 641, the electrode 615, and the separator 642 by mixing a gelling agent or a polymer material, a cross-linking agent, and a binder, a laminate of the porous film is obtained, The water phase can be gelled or cured. Also, after winding, the non-aqueous phase may be gelled or cured.

Further, for example, as shown in Fig. 9C, when each non-water phase 612, 622, and 632 exists as a layer between the electrode 614 and the electrode 615, and the layer has a sufficient thickness, The separators 641 and 642 can be omitted because there is no possibility that the electrode 614 and the electrode 615 are in contact with each other even if the separators 641 and 642 are not provided on the electrode surface.

Each of the first non-aqueous phase (612), the second non-aqueous phase (622) and the third non-aqueous phase (632) may contain an enzyme body containing one or more kinds of the same enzymes, Or the like. When the enzyme reaction is carried out for each of the first non-aqueous phase 612, the second non-aqueous phase 622 and the third non-aqueous phase 632, that is, It is desirable to take the following measures.

In order to surely perform the enzymatic reaction in the first non-aqueous phase 612, the portion including the first non-aqueous phase 612 in the laminated body of the porous film is surrounded by the second non- It is preferable to set the width of the portion where the first non-aqueous phase 612 is provided so as to cover a portion of the portion including the first non-aqueous phase 612. That is, it is preferable that the layers including the first non-aqueous phase 612 partially overlap.

Likewise, in order to reliably perform the enzymatic reaction in the second non-aqueous phase 622, the portion including the second non-aqueous phase 622 in the laminated body of the porous film is a portion of the portion including the third non- It is preferable to set the width of the portion where the second non-aqueous phase 622 is provided so as to cover a portion of the portion including the second non-aqueous phase 622 even after the layer is surrounded. That is, the layers including the second non-aqueous phase 622 are preferably partially overlapped.

Thus, it is possible to ensure that each reaction step of the multi-step enzyme reaction is carried out in the order of sequence, by arranging different enzyme bodies contained in each of the non-aqueous phases to be dispersed or supported so as to be arranged in the radial direction of the winding shape of the non- .

In addition, in the case of performing the multistage enzyme reaction, in order to efficiently progress the production of the final product by the multistage enzyme reaction, the volume of each non-aqueous phase and the amount of the non- The concentration of the enzyme in the non-aqueous phase can be appropriately adjusted.

In the carbon dioxide immobilization apparatus 600 shown in Fig. 8, carbon dioxide can be supplied to the non-aqueous portion 601 by flowing the gaseous phase 611 in a gas flow path located on the outer periphery of the non-water upper portion 601 . The carbon dioxide is reduced by an enzyme reaction in the non-aqueous upper portion 601, and a reaction product is produced. The reaction product can be recovered from the non-aqueous portion 601 by allowing the water phase 633 to flow in the liquid flow path in contact with the center of the non-aqueous portion 601.

The carbon dioxide immobilization apparatus shown in Fig. 8 can generate a reaction product such as fuel from carbon dioxide by a multistage enzyme reaction. For example, in the same manner as in Fig. 7, methanol can be produced from carbon dioxide by a multistage enzymatic reaction.

Fig. 10 shows a schematic view of a carbon dioxide immobilization apparatus according to another embodiment of the first embodiment according to the embodiment.

The carbon dioxide immobilization apparatus 700 shown in Fig. 10 is an example of a batch type apparatus, unlike the flow type apparatus shown in Figs. This carbon dioxide immobilization apparatus 700 includes a gas phase 711, a non-aqueous phase 712, and a water phase 713. These phases are housed in the cell body C10.

The vapor phase 711 contains a gas containing carbon dioxide. In Fig. 10, the chamber accommodating the gas phase 711 is provided in the cell main body C10. The chamber accommodating the gas phase 711 may not be provided in the cell main body C10. For example, the non-aqueous phase 712 may be exposed to a gas containing carbon dioxide such as atmospheric air, and the gas may be vapor phase 711. When the chamber accommodating the vapor phase 711 is installed in the cell main body C10, for example, the gas introduction port or the vent hole communicated with the gas chamber 711 is provided in the cell main body C10, (711).

The non-aqueous phase 712 is an ionic liquid, an enzyme body 11, a mediator (a reducing body 14a and an oxidant body 14b, for example) similar to the first block 110 in the apparatus shown in Fig. )). In addition, the enzyme body 11 shown in Fig. 10 contains an enzyme 12 therein.

The non-aqueous solution 712 includes a cathode electrode 715 for reducing the oxidant 14b of the mediator to the reducing agent 14a of the mediator, an anode electrode 714, a cathode electrode 715, (Not shown) for controlling the voltage (or potential) applied to the cell 714.

Instead of the cell voltage control unit, a current control unit for controlling the current flowing between the anode electrode 714 and the cathode electrode 715 may be used. Alternatively, an electric control unit which can also serve as the cell voltage control unit and the current control unit may be used.

The cathode electrode 715 and the anode electrode 714 are required to be in contact with the non-aqueous solution 712 and are not limited to the arrangement shown in Fig. 10 unless they are in contact with each other and electrically short-circuited. For example, the positions where these electrodes are provided may be the interface between the gas phase 711 and the non-aqueous phase 712, or the interface between the non-aqueous phase 712 and the aqueous phase 713. It is preferable to use a porous electrode material for the cathode electrode 715 and / or the anode electrode 714 when the cathode electrode 715 and / or the anode electrode 714 are provided at the interface of the other phases.

Since the non-aqueous phase 712 as an ionic liquid has a specific gravity larger than that of the aqueous phase, even when a porous support film or a porous substrate is provided between the non-aqueous phase 712 and the aqueous phase 713 do. Further, as shown in the figure, the separator 741 may be provided together with the separator 741 or separately.

The water phase 713 includes an extraction liquid for extracting the first reaction product 15 from the non-aqueous phase 712. It is also preferable to provide a mechanism (not shown) for mechanically stirring the extract.

In the carbon dioxide immobilization apparatus 700 of Fig. 10, carbon dioxide supplied from the gas phase 711 to the non-aqueous phase 712 is adsorbed to the enzyme (for example, 12), and the first reaction product 15 is produced. The first reaction product 15 is supplied to the water phase 713.

The water phase 713 can be recovered from an outlet provided at the lower portion of the cell main body C10 after the concentration of the first reaction product 15 reaches a predetermined value.

The enzyme reaction for reducing carbon dioxide in the non-aqueous phase (712) may be a single step or a multi-step enzyme reaction.

In the case of a single step reaction, formate is produced as the first reaction product (15) by using formate dehydrogenase as the enzyme (12), for example.

In the case of a multistage reaction, a plurality of other enzyme bodies are included in the non-aqueous phase 712. For example, when methanol is produced by reduction of carbon dioxide by a three-step reaction, a first enzyme body containing formate dehydrogenase, a second enzyme body containing formaldehyde dehydrogenase, and a third enzyme body containing alcohol dehydrogenase Is included in the non-award 712.

In this example, the carbon dioxide supplied to the non-aqueous phase 712 is reduced by the first enzyme body, and formic acid is produced. Formic acid rapidly moves to the second enzyme form and is reduced to formaldehyde. Similarly, formaldehyde quickly migrates to the third enzyme body and is reduced to methanol as the final product.

In the case of using a multistage reaction using a plurality of different enzyme bodies, it is preferable that the extract in the water phase 713 is adjusted so that the final product can be selectively extracted. For example, in the above example, it is preferable to adjust the extract so that methanol is selectively supplied to the water phase 713.

The first block 110, the second block 120 and the third block 130 included in the carbon dioxide immobilizer 100 shown in Fig. 1 are replaced by the carbon dioxide immobilizer 700 of Fig. 10 . In this case, the enzymes to be included in the non-aqueous phase 712 are appropriately selected according to the enzyme reaction performed in each block.

11A and 11B are schematic views of single cells used in an example of the stacked carbon dioxide immobilization apparatus according to the embodiment.

11A is a schematic plan sectional view of the single cell type carbon dioxide immobilization apparatus 800 viewed from below. Fig. 11B shows a schematic cross-sectional view of the single cell type carbon dioxide immobilization apparatus 800 viewed from the side.

In the monocell type carbon dioxide immobilization apparatus 800 of Figs. 11A and 11B, the gas phase 811, the electrode 814 (anode electrode), the non-aqueous phase 812, the electrode 815 (cathode electrode) (813) are arranged in order from the bottom. In the illustrated example, each phase and each electrode has a planar shape.

The electrode 814 is a porous electrode, and for example, carbon paper can be used as the electrode 814. [ The electrode 814 is connected to an electrode plate 861 serving as a flow path and a lead wire of the vapor phase 811. In the illustrated example, a plurality of partitions defining the flow path of the vapor phase 811 are formed between the electrode 814 and the electrode plate 861. The partition may be omitted.

11A, when a gas containing carbon dioxide is introduced into the channel of the vapor phase 811 from the gas inlet 51, the gas exits the gap between the electrode plate 861 and the electrode 814, And is discharged from the gas discharge port 52. [0054] When carbon dioxide passes through the gap between the electrode plate 861 and the electrode 814, at least a part of the carbon dioxide passes through the electrode 814 and is supplied to the non-aqueous phase 812, It becomes the substrate of the reaction.

As the medium of the non-aqueous phase (812), it is preferable to use an ionic liquid or the like capable of selectively absorbing carbon dioxide. In this case, a gas other than carbon dioxide, for example, which is not absorbed by the non-aqueous phase 812, is discharged from the gas outlet 52.

The electrode 815 is a porous electrode. For example, carbon paper can be used as the electrode 815. According to another example, the electrode 815 is a sheet-like electrode or a porous electrode provided with a plurality of slits. The electrode 815 is connected to an electrode plate 862 serving as a flow path and a lead wire of the water phase 813.

11A, when the extract liquid is introduced into the channel of the water phase 813 from a liquid inlet (not shown), the extracted liquid is supplied to the electrode plate 862 and the electrode 815, Flows out along the plane direction, and is led out from the liquid outlet.

The carbon dioxide supplied from the gas phase 811 to the non-aqueous phase 812 is reduced by an enzyme reaction to produce a reaction product. The reaction product is supplied to the water phase 813 and recovered.

Further, a temperature sensor may be provided in the single cell (carbon dioxide immobilizer 800), or a heat insulating material 870 may be provided on the outside of the single cell. The temperature of the single cell can be measured by the temperature sensor, and the temperature can be controlled based on the measurement result, for example, by a temperature control mechanism so as to be in an appropriate condition for the enzyme reaction. Further, by providing the heat insulating material 870, the enzyme reaction can be performed under more stable temperature conditions.

11A and 11B show an example in which a heat insulating material 870 is provided. The shape of the heat insulating material 870 is not particularly limited, but may have, for example, a slab-shaped form. The insulating material 870 may be omitted.

Each phase and each electrode are integrated by a jig J1. For the purpose of preventing electrical shorting, for example, the jig J1 may include a material having electrical insulation. In the case of using a conductive material such as a metal or an alloy as the jig J1 in consideration of the properties such as strength or the like, an insulating film is provided on the surface of the jig J1 to prevent electrical short- .

The partition in the vapor phase 811 is an example of the spacer 816 shown in the figure. The shape of the spacer 816 is not limited to the shape of the partition wall shown in the figure. The spacer 816 may be of a shape other than the partition wall. For example, the spacer 816 may also serve to prevent deformation of the electrode 814 due to stress such as pressure. However, if the electrode 814 has sufficient strength, the spacer 816 may be omitted .

The spacer 816 may be formed of, for example, a conductive material. In this case, the electrode 814 and the electrode plate 861 can be electrically connected through the spacer 816. [ Alternatively, as the electrode plate 861, for example, a protrusion can be used instead of the spacer 816 by using a protrusion formed by molding. In this case, the electrode 814 and the electrode plate 861 are directly electrically connected by the projections.

Instead of electrically connecting the electrode 814 and the electrode plate 861 through the spacer 816, a conductor or the like for electrical connection may be separately provided. In this case, it is preferable to use an insulating material as the material of the spacer 816. [ In addition, it is preferable to suitably select the material of the spacer 816 in accordance with the temperature and the temperature of the gas supplied to the vapor phase 811.

Examples of the material that can be used for the spacer 816 include materials having high conductivity such as stainless steel, nickel, copper, aluminum, tungsten, conductive polymer, and graphite. Examples of other materials include non-conductive materials such as plastic, ceramics and glass.

By defining the flow path in the gas phase 811 by the spacer 816, the time during which the flowing gas flows along the surface of the electrode 814 can be sufficiently long. For example, the spacer 816 is provided as a partition wall so that the flow path from the gas introduction port 51 to the gas discharge port 52 is long, and the gas is supplied from the circulated gas through the electrode 814 to the non- It is possible to increase the amount of carbon dioxide. The shape and the arrangement of the spacer 816 are not limited to those shown in the drawings, as long as they can secure a flow path for supplying carbon dioxide to the non-aqueous phase 812. For example, the shape of the spacer 816 may be a dot shape instead of a slit shape. It is preferable to appropriately design the shape and the arrangement of the spacer 816 in accordance with conditions such as the state of the supply source of the gas to be introduced into the gas inlet 51 and the conditions such as the flow rate, temperature and pressure of the gas to be introduced.

A plurality of spacers 817 defining the flow path of the extraction liquid can be provided between the electrode 815 and the electrode plate 862 in the water column 813. [ The spacer 817 can be formed of, for example, a conductive material. In this case, the electrode 815 and the electrode plate 862 can be electrically connected through the spacer 817. [ Alternatively, as the electrode plate 862, for example, a protrusion can be used instead of the spacer 817 by using a protrusion formed by molding. In this case, the electrode 815 and the electrode plate 862 are directly electrically connected by the projection.

Instead of electrically connecting the electrode 815 and the electrode plate 862 through the spacer 817, a conductor or the like for electrical connection may be separately provided. In this case, it is preferable to use an insulating material as the material of the spacer 817. In addition, it is preferable to appropriately select the material of the spacer 817 in accordance with the components of the extract.

Examples of the material that can be used for the spacer 817 include materials having high conductivity such as stainless steel, nickel, copper, aluminum, tungsten, conductive polymer, and graphite. Examples of other materials include non-conductive materials such as plastic, ceramics and glass.

By defining the flow path in the water phase 813 by means of the spacer 817, the time during which the flowing liquid flows along the surface of the electrode 815 can be sufficiently long. For example, by providing the spacer 817 like a partition wall so that the flow path from the liquid inlet to the liquid outlet is long, the amount of the reaction product extracted from the non-aqueous phase 812 can be increased by the liquid extract. The shape and arrangement of the spacer 817 are not limited as long as they can secure a flow path through which the reaction product can be extracted from the non-aqueous phase 812. For example, the shape of the spacer 817 may be a slit shape or a dot shape. It is preferable to appropriately design the shape and arrangement of the spacer 817 in accordance with conditions such as the flow rate, temperature and pressure of the extract liquid to be introduced into the liquid inlet.

The spacer 817 may also serve to prevent deformation of the electrode 815 due to stress such as pressure. If the electrode 815 has sufficient strength, the spacer 817 may be omitted. On the other hand, when the spacer 817 is omitted, it is difficult to control the flow of the extract liquid because there is no flow path of the extract liquid. Therefore, it is preferable to provide the spacer 817 to define the flow path of the extract liquid in the water phase 813.

Further, for example, a gasket including a material such as resin may be provided at the ends of the electrode plate 861 and the electrode plate 862. It is possible to prevent leakage of the carbon dioxide or the extract liquid in the single cell by the gasket.

When the single cell type carbon dioxide immobilization apparatus 800 shown in Figs. 11A and 11B is stacked, the stacked-type carbon dioxide immobilization apparatus 900 shown in Fig. 12 is obtained. In Fig. 12, the carbon dioxide immobilization apparatus 800 shown in Figs. 11A and 11B is simplified and drawn. In Fig. 12, reference numeral 871 denotes a gasket.

The stacked-layer carbon dioxide immobilizer 900 shown in Fig. 12 includes a plurality of single cells (carbon dioxide immobilizer 800). These single cells are stacked in the thickness direction to form a stacked structure, and are integrated by jigs J2 and J3. Between the adjacent single cells, an electrically insulating sheet (not shown) is provided to prevent electrical contact between the electrode plate 861 of one single cell and the electrode plate 862 of the other single cell.

For example, a plurality of single cells may be stacked on a jig J3 provided along the stacking direction in a state where jigs J2 are arranged at both ends in the stacking direction of the stacked structure and single cells stacked therebetween are arranged And the jigs J2 at both ends are connected to each other. The jig J2 may be, for example, a flat member. The jig J3 may be, for example, a columnar member. For the purpose of preventing electrically shorting, for example, the jigs J2 and J3 may include a material having electrical insulation. In consideration of the strength and other properties, for example, when a conductive material such as a metal or an alloy is used as the jigs J2 and J3, an insulating film is provided on the surfaces of the jigs J2 and J3, It is preferable to prevent short-circuiting.

The gas inlet 51 and the gas outlet 52 of each single cell are connected to a common gas introduction path and a common gas discharge path (both not shown). Alternatively, one single-cell gas outlet port 52 may be connected to the gas inlet port 51 of the other single cell to constitute a gas flow path connected in series. In this manner, by changing the connection method of the gas flow path, it is possible to flow the gas phase to all the single cells simultaneously or to make the gas phase flow sequentially to each single cell.

The liquid inlet and the liquid outlet of each single cell are connected to a common liquid introduction path and a common liquid lead-out path (both not shown). Alternatively, one single cell liquid outlet may be connected to the liquid inlet of the other single cell to constitute a series connected liquid channel. Thus, by changing the connection method of the liquid flow path, it is possible to simultaneously flow the extractant (water phase) to all of the single cells or sequentially flow the extract liquid (water phase) into each single cell.

Further, in the stack including these single cells, the electrode plates 861 in each single cell are electrically connected to each other by the electrode lead line 961. Similarly, the electrode plates 862 of the plurality of single cells are electrically connected to each other by the electrode lead 962. [ When the electrode lead line 961 and the electrode lead line 962 are electrically connected to the cell voltage control unit and a voltage is applied between the electrode lead lines 961 and 962 by the cell voltage control unit, 862 are applied with a voltage.

The electrode lead line 961 and the electrode lead line 962 may be electrically connected to the current control unit instead of being connected to the cell voltage control unit. The current control unit can control the current flowing between the electrode plates 861 and 862 of each single cell, for example. Alternatively, an electric control unit which can also serve as the cell voltage control unit and the current control unit may be used.

In Fig. 12, the electrode plates 861 in each single cell are electrically connected in parallel, but the electrode plates 861 may be electrically connected in series. Similarly, although the electrode plates 862 are electrically connected in parallel in Fig. 12, the electrode plates 862 may be electrically connected in series.

According to the apparatus of this constitution, carbon dioxide can be fixed with high efficiency.

In the illustrated example of the carbon dioxide immobilization apparatus, the mode of regenerating the mediator by the electrochemical method has been described in detail. When the mediator is regenerated by a method other than the electrochemical method, the cathode electrode and the anode electrode may be omitted. Alternatively, the cathode electrode that also serves as the porous film and the anode electrode that also serves as the porous film may be replaced with a porous film or spacer that does not function as an electrode. When the cathode electrode and the anode electrode are omitted or replaced, the electrical control unit can be omitted.

Also, the method of reproducing the mediator may be different between the respective blocks (for example, the first block 110, the second block 120 and the third block 130 shown in Fig. 1). For example, an electrochemical method may be used for the first block and the second block, and an enzyme method may be used for the third block. In this case, each of the first block and the second block includes a cathode electrode and an anode electrode which are in contact with the non-aqueous solution. The third block includes, for example, an enzyme body that catalyzes an enzyme reaction to regenerate the mediator. The cathode electrode and the anode electrode of the third block may be omitted or replaced.

The apparatus for immobilizing carbon dioxide according to the first embodiment comprises an enzyme body for catalyzing a reduction reaction of an ionic liquid and carbon dioxide or a reduction product thereof and a mediator acting as a reducing agent or a coenzyme in the reduction reaction, A non-aqueous phase which is supplied with a reducing product to produce a reaction product by the reduction reaction, and an aqueous solution containing water, wherein the reaction product is supplied from the non-aqueous phase. According to the apparatus of this constitution, carbon dioxide can be fixed with high efficiency.

(Second Embodiment)

According to the second embodiment, there is provided a fuel production system including a carbon dioxide supply unit, a fuel generation unit, and an extractor recovery unit.

Fig. 13 shows an example of the fuel production system according to the second embodiment.

By providing the carbon dioxide immobilizer according to the first embodiment in the fuel generator of the system shown in Fig. 13, the production of fuel from carbon dioxide can be automatically controlled.

The dotted lines (external electric lines E1 to E6) in Fig. 13 represent electric system circuits. On the other hand, the solid lines (L1 to L5) in Fig. 13 represent a gas phase or liquid phase piping system.

Each of the wirings E1 to E6 in the electric system circuit functions as an external electric line for supplying electric power and functions as an external signal line for transmitting signals for controlling the respective members such as an electric signal.

The control unit 91 and the cell voltage control unit are connected through the external electric lines E2 and E3 to externally apply the voltage to the carbon dioxide immobilizer installed in the fuel generating unit 82. [ The control unit 91 and the temperature control unit 94 are connected to the fuel generating unit 82 through the external electric lines E2 and E4.

The control unit 91 of the electric system system 90 controls the cell voltage control unit so that the voltage applied to the carbon dioxide immobilizer is determined by the temperature condition information from the sensor provided in the carbon dioxide immobilizer and the carbon dioxide supply information of the carbon dioxide supply unit 81, Indicate conditions. The control unit 91 of the electrical system 90 instructs the extraction liquid supply unit 83 to supply the condition of the supply flow rate of the extract liquid in accordance with the carbon dioxide supply information of the carbon dioxide supply unit 81 and the like. The control unit 91 instructs the temperature control unit 94 to control the temperature of the fuel generation unit 82. [

The cell voltage control unit may be replaced with a current control unit. In this case, the control section 91 instructs the current control section to condition the current flowing in the carbon dioxide immobilizing device.

The illustrated electrical control unit 95 may be a cell voltage control unit for controlling the voltage applied to the carbon dioxide immobilization apparatus. Alternatively, the electric control unit 95 may be a current control unit for controlling the current in the carbon dioxide immobilization apparatus. The electric control unit 95 may be provided with a mode functioning as a cell voltage control unit and a mode functioning as a current control unit. The electric control unit 95 can switch the operation mode between the mode as the cell voltage control unit and the mode as the current control unit based on an instruction from the control unit 91. [

The carbon dioxide supply unit 81 may have a function of controlling the pressure of the gas containing carbon dioxide. For example, the control unit 91 detects the pressure of the gas in the carbon dioxide supply unit 81 and instructs the pressure control through the external electric line E5 (external signal line) as necessary.

In the extraction liquid recovery unit 84, the fuel is recovered from the extraction liquid and the pH of the extraction liquid is adjusted. The extract liquid is then supplied to the extract liquid supply unit 83 and reused.

The extraction liquid supplier 83 temporarily stores the liquid supplied from the liquid recovery unit 84 and supplies the liquid to the fuel generator 82 at a predetermined flow rate in response to a command from the controller 91 do.

Further, by using the extract liquid supply tank 85, the condition of the extract liquid of the extract liquid supplier 83 can be changed and adjusted.

The fuel production system according to the second embodiment includes the fuel generation section including the carbon dioxide immobilization apparatus according to the first embodiment. Therefore, this system can fix carbon dioxide with high efficiency.

[Example]

Hereinafter, an example will be described as an example of a specific design of the carbon dioxide immobilization apparatus according to the embodiment.

(Example 1)

The carbon dioxide immobilizer of the first embodiment is a carbon dioxide immobilizer including the first block, the second block and the third block, like the carbon dioxide immobilizer 100 shown in Fig. Further, in the carbon dioxide immobilization apparatus of Example 1, as an example of a reaction for immobilizing carbon dioxide, methanol as a fuel is produced from carbon dioxide.

In Example 1, methanol is produced by the following three-step enzyme reaction.

Hereinafter, the carbon dioxide immobilization apparatus of the first embodiment will be described with the same structure as that of the carbon dioxide immobilizer 100 of FIG.

The first enzyme reaction is a reaction in which formate dehydrogenase (Fe _ate DH: FDH) is used as an enzyme and formic acid or formate is produced from carbon dioxide, which is a substrate. The first enzyme reaction is generated, for example, in the non-aqueous phase 112 in the first block 110 shown in FIG.

The second enzymatic reaction is performed in the second block 120 and the formaldehyde is reacted with formic acid or formate produced in the first block 110 as a substrate in the presence of the enzyme Formaldehyde dehydrogenase (F _ald DH) .

The third enzyme reaction is performed in the third block 130, and formaldehyde generated in the second block 120 is used as a substrate to produce methanol in an enzyme reaction in the presence of the enzyme Alcohol dehydrogenase (ADH).

Ion gel containing 1-Ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) amide (abbreviation: EMIMTFSI) was used as the non-aqueous phase 112 of the first block 110.

The enzyme body 11 involved in the first enzyme reaction was obtained by impregnating a silica gel having dispersed and immobilized formate dehydrogenase (Fe _ate DH) with 3 mM NADH and pH 7, 0.1 M phosphate buffer solution. The silica gel used here was porous spherical silica particles having mesopores, with an average particle diameter of 0.3 mu M and an average pore diameter of 16 nm. The obtained enzyme body (11) was dispersed in EMIMTFSI which is the medium of the first non-aqueous phase.

In addition, the EMIMTFSI containing F _ate DH / silica gel as the enzyme (11), and were gel tetra-armed poly (ethylene glycol) ions. F _ate DH / silica gel is uniformly dispersed in the mesh of ionic gel of EMIMTFSI. In this manner, an ion gel membrane containing the enzyme body 11 was obtained as the non-aqueous phase 112 of the first block 110.

An ion gel membrane of EMIMTFSI including the enzyme body 11 was sandwiched between carbon paper as a pair of porous electrodes. As the carbon paper, one modified with Poly (Neutral red) was used. The first block 110 was disposed such that one porous electrode (anode electrode 114) was in contact with the carbon dioxide flow path side and the other porous electrode (cathode electrode 115) was in contact with the water side.

As the fuel extraction liquid contained in the water phase 113 of the first block 110, a phosphate buffer solution of pH 7 and a concentration of 50 mM was used. In the non-aqueous phase (112) containing the enzyme body (11), fuel generated by the enzyme reaction is extracted into the aqueous phase (113).

An ion gel containing an enzyme body 21 containing an enzyme Formaldehyde dehydrogenase (F _ald DH) was used for the non-aqueous phase 122 related to the second enzyme reaction. An ion gel in which the enzyme bodies 21 were dispersed was obtained in the following manner.

(Χ _PIL = AIL / PIL = 0.7) of AIL [C ₈ mIm ⁺ ] [TFSA ^- ] and PIL [C ₈ ImH ⁺ ] [TFSA ^- ] was used as an ionic liquid which is a precursor of ion gel. [C ₈ mIm ⁺ ] [TFSA ^- ] is a hydrophobic ionic liquid, and [C ₈ ImH ⁺ ] [TFSA ^- ] is a hydrophilic ionic liquid. [C ₈ ImH ⁺ ] [TFSA ^- ] also serves as an auxiliary surfactant.

AOT was added to the mixed solution, and AOT (0.07M) was dispersed by stirring for 20 hours. [C ₈ mIm ⁺ ] [TFSA ^{- 1} ] as a non-aqueous phase was obtained by adding a dilute buffer [50 mM phosphoric acid pH = 7] containing F _ald DH as an enzyme and 3 mM NADH as a mediator as a water solvent and stirring for 1 hour, ] And [C ₈ ImH ⁺ ] [TFSA ^- ] in the mixed solution of [C ₈ ImH ⁺ ] and [C ₈ ImH ⁺ ] [TFSA ^- ]. F _ald DH as an enzyme is solubilized in the water pool of the thus obtained reverse micelle (second enzyme body).

Subsequently, the mixed liquid of the ionic liquid was made into a state in which the enzyme bodies were dispersed at a temperature of 40 ° C to 50 ° C, a proper amount of gelatin powder was added thereto, and the mixture was vigorously stirred for about 30 minutes. Subsequently, the mixed solution was cooled to 30 DEG C with stirring, and the stirring was continued until the solution became very dense and homogeneous. The resulting suspension was allowed to stand at room temperature until it became a transparent gel.

By the above process, the gelatin enters the water pool of the enzyme body (reverse micelle) and gels there. Further, since an intermolecular network is formed by the gelatin gelled in the water pool, the non-aqueous phase containing the enzyme body gels. Further, by allowing the turbid solution to stand at room temperature, refolding of the thermally denatured protein (gelatin, _Fodd DH) can be further performed.

Reversed micelles containing the enzyme Alcohol dehydrogenase (ADH) were used for the enzyme bodies (enzyme bodies 31) involved in the third enzyme reaction. This enzyme complex was treated with a mixture of [C ₄ ImH ⁺ ] [TFSA ^- ] (χ _PIL ^- ), which is a non - aqueous aprotic ionic liquid (AIL) [C ₈ mIm ⁺ ] [TFSA ^- ] and a protonic ionic liquid = AIL / PIL = 0.4). Also, [C ₈ mIm ⁺ ] [TFSA ^- ] is a hydrophobic ionic liquid and [C ₄ ImH ⁺ ] [TFSA ^- ] is a hydrophilic ionic liquid. [C ₄ ImH ⁺ ] [TFSA ^- ] also serves as an auxiliary surfactant.

The non-aqueous phase (132) containing the enzyme substance (31) was obtained in the following manner.

Bis (2-ethylhexylcarbonyl) -1-ethanesulfonate (Aerosol) was added to a mixture of [C ₈ mIm ⁺ ] [TFSA ^- ] and [C ₄ ImH ⁺ ] [TFSA ^- OT: AOT) was added, and AOT (0.07M) was dispersed by stirring for 20 hours. Subsequently, a dilute buffer [50 M phosphoric acid, pH = 7] (0.02 M PBS) containing Alcohol dehydrogenase (ADH) as an enzyme and a mediator NADH was added as an aqueous solution and stirred for 1 hour, The water containing an enzyme body comprising AOT and [C ₄ ImH ⁺ ] [TFSA ^- ] in a mixture of [C ₈ mIm ⁺ ] [TFSA ^- ] and [C ₄ ImH ⁺ ] [TFSA ^- ] Micelles.

By the above injection method, reversed micelles in which ADH was solubilized in a water pool were formed. In addition, reverse micelles were formed as enzyme bodies, and the reverse micelles were dispersed in the non-aqueous medium.

It is possible to sufficiently supply NADH to the enzyme reaction in the water pool of the reverse micelle as the third enzyme body (enzyme body 31) or in the non-aqueous phase, so that the enzyme reaction in the third block 130 can proceed smoothly . Methanol generated in the enzymatic reaction is extracted into an extract (water phase) contacting the porous electrode (cathode electrode 135).

In the non-aqueous phase of each block, an anode electrode was disposed. In addition, reference electrodes were disposed at appropriate positions in the non-aqueous phase of each block (not shown).

Methanol is conveyed to a separator (not shown) by an external circulation pipe, and methanol is separated and recovered as a final fuel. Thereafter, the pH of the extract is adjusted and then introduced into the water phase 113 from the inlet port communicating with the water phase 113 of the first block 110.

NADH is used as a mediator of the above three enzymatic reactions. NADH is dispersed in each non-aqueous phase and each enzyme body. NADH is oxidized to NAD &lt; ⁺ &gt; by the respective enzymatic reactions in the above three blocks. Oxidized NAD ⁺ is reduced again to NADH in the carbon paper (cathode electrode) modified with Poly (Neutral Red) by electropolymerization in each block. Further, NADH can be separately added to the non-aqueous phase in a supersaturated state.

In the carbon dioxide immobilization apparatus of the first embodiment, by increasing the pressure of the carbon dioxide introduced into the gaseous phase 111 of the first block 110 (for example, about 1.5 MPa) or by accelerating the gas sending speed of the carbon dioxide, Can be increased.

In addition, proton ions required for the above three enzymatic reactions can be supplied from the extract.

By using the carbon dioxide immobilization apparatus of Example 1, methanol was obtained from carbon dioxide at a high fuel conversion efficiency.

(Example 2)

The carbon dioxide immobilization apparatus of Example 2 is an apparatus for producing methanol as a fuel from carbon dioxide by a two-step enzyme reaction.

The carbon dioxide immobilizer according to the second embodiment includes a plurality of adjacent non-aquifers, like the carbon dioxide immobilizer 400 shown in Fig. 6 shows three non-water phase 412, 422, and 432 including the enzyme body, respectively. However, the carbon dioxide immobilizer according to the second embodiment includes two non-water phase bodies each containing the enzyme body, . That is, the carbon dioxide immobilizer according to the second embodiment has a smaller number of non-receivers than the carbon dioxide immobilizer 400. [ Further, in the carbon dioxide immobilization apparatus of the second embodiment, the number of the electrodes 415, 425, or 435 can be reduced by one. Hereinafter, the carbon dioxide immobilization apparatus of the second embodiment will be described with reference to FIG. 6, in which the third non-aqueous phase 432 and the electrode 435 are omitted.

In Example 2, methanol is produced by the following two-step enzyme reaction.

In the above formula, PQQ is pyrroloquinoline quinone. The molecular structure thereof is shown below.

PQQ acts as a mediator in the enzymatic reaction by Formate dehydrogenase (F _ate DH) or Methanol dehydrogenase (MDH). When PQQ participates in the enzymatic reaction, it is oxidized from reduced PQQ _red to oxidized PQQ _ox .

PQQ _ox is reduced to PQQ _red again in the electrode 415 or the electrode 425 provided in the non-aqueous phase containing the enzyme body, and participates in the enzyme reaction.

The first enzymatic reaction in Example 2 is a reaction in which formate dehydrogenase (Fe _ate DH) is used as an enzyme and formic acid is produced from carbon dioxide as a substrate.

The first enzyme reaction occurs in the first non-aqueous phase (412).

The second enzyme reaction is carried out in the second non-aqueous phase 422, and methanol is produced in the presence of enzyme (MDH) using formic acid produced in the first non-aqueous phase as a substrate.

In the carbon dioxide immobilization apparatus of Example 2, a fourth non-aqueous phase 402 not containing an enzyme body is provided adjacent to the first non-aqueous phase 412 containing an enzyme body, as in FIG. The fourth non-aqueous phase (402) is in contact with the vapor phase (411) contained in the air flow channel for the carbon dioxide. The carbon dioxide introduced into the gas phase 411 is once absorbed by the fourth non-aqueous phase 402 and then introduced into the first non-aqueous phase 412 containing the first enzyme body. In addition, the fourth non-aqueous phase (402) may be omitted.

An electrode 414 is provided in the fourth non-aqueous phase 402. When the fourth non-aqueous phase 402 is omitted, the electrode 414 may be placed in contact with the first non-aqueous phase 412 and not in contact with the electrode 415.

A separator 441 is provided between the fourth non-aqueous phase 402 and the first non-aqueous phase 412 to prevent diffusion of the enzyme substance contained in the first non-aqueous phase 412. Further, a separator 442 is provided between the second non-aqueous phase 422 and the aqueous phase 433.

An ion gel containing 1-Ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) amide (abbreviation: EMIMTFSI) was used for the fourth non-aqueous phase 402. In this ion gel, the enzyme substance is not dispersed.

As the first enzyme involved in the first enzyme reaction, a silica gel containing Formate dehydrogenase (Fe _ate DH) was used, which was further impregnated with 5 mM PQQ and pH 7, 0.1 M phosphate buffer. This enzyme body was dispersed in EMIMTFSI as the first non-aqueous phase (412). Next, EMIMTFSI containing the first enzyme, FDH / silica gel, was also made into a tetra-armed poly (ethylene glycol) ion gel.

As the second enzyme involved in the second enzyme reaction, a silica gel containing methanol dehydrogenase (MDH) was further impregnated with 5 mM PQQ and pH7, 0.1 M phosphate buffer. This enzyme body is dispersed in the second non-aqueous phase (422) EMIMTFSI.

(The first non-aqueous phase 412) of the EMIMTFSI including the fourth non-aqueous phase 402, the separator 441 and the electrode 414, the first enzyme body, the electrode 415, and the second enzyme body An enzyme membrane electrode fuse formed by stacking EMIMTFSI (second non-water phase 422), an electrode 425 and a separator 442 in this order was installed in the cell body C10 to fabricate the carbon dioxide immobilization device of Example 2 Respectively. Carbon paper was used for the electrode 415 and the electrode 425.

As the electrode 414, carbon paper was used.

With this apparatus, it was possible to produce methanol as fuel from carbon dioxide with high efficiency.

(Example 3)

The carbon dioxide immobilizer according to the third embodiment is an apparatus for producing methanol as a fuel from carbon dioxide by a two-step enzyme reaction in the same manner as the carbon dioxide immobilizer according to the second embodiment.

In Example 3, as in Example 2, methanol is produced by an enzymatic reaction with two-step enzyme reaction formate dehydrogenase (Fe _ate DH) and methanol dehydrogenase (MDH). The mediator, the non-aqueous phase and the extract of Example 3 were the same as those used in Example 2.

In Example 3, unlike the lamination method of Example 2, a wound type enzyme membrane electrode fusion material as shown in Fig. 8 is produced. However, unlike the non-aqueous portion 601 shown in Fig. 8 and Figs. 9A to 9C, which includes the non-aqueous phase separated into three, the spiraled type enzyme membrane electrode fuse of Example 3 includes a single non-aqueous phase. Further, in Example 3, two enzymes F _ate DH and MDH are contained in the same enzyme body, and this enzyme body is dispersed in the single non-aqueous phase.

As the porous electrodes (electrodes 614 and 615), carbon cloth was used. Further, a separator was provided on one of the porous electrodes.

A non-aqueous phase containing a porous electrode, an enzyme body, another porous electrode, and an enzyme membrane electrode fused body in which a separator was formed in order were wound so that the separator was outside. Further, at the center of the winding of the enzyme membrane electrode fuselage, a cavity was made to be a channel for flowing the extract solution.

A porous supporter (inner tube 653) for supporting the enzyme membrane electrode fusion substance was further provided in the center channel of the enzyme membrane electrode fusion body. And an extracting liquid for extracting the fuel is caused to flow through the central passage.

On the other hand, a porous supporter (intermediate tube 652) for supporting the enzyme membrane electrode fusion body was further provided on the outer periphery of the wound body of the enzyme membrane electrode fusion body. Then, a space as a channel for sending carbon dioxide was provided, and an enzyme membrane electrode fusion body including a support body was provided in an outer casing (outer casing 651).

Carbon dioxide is introduced from the outer circumferential flow path. Carbon dioxide introduced from the outer circumferential channel reaches the layer of the non-aqueous phase including the enzyme body through the porous supporter supporting the enzyme membrane electrode fuselage. Thus, carbon dioxide participates in an enzyme reaction as a substrate of an enzyme reaction in a non-aqueous phase containing an enzyme body. In the non-aqueous phase, an enzymatic reaction is carried out in two stages starting with carbon dioxide as a first substrate, and methanol as a fuel is finally produced.

The produced methanol is finally extracted through the porous support of the inner circumference of the enzyme membrane electrode fusible material and flowing through the center channel.

By using the carbon dioxide immobilization apparatus of Example 3, methanol was obtained from carbon dioxide at higher fuel conversion efficiency.

(Example 4)

The carbon dioxide immobilizer of Example 4 is a batch carbon dioxide immobilizer such as the carbon dioxide immobilizer 700 shown in Fig. 10, and is a device for producing methanol as a fuel from carbon dioxide.

Hereinafter, the carbon dioxide immobilizer according to the fourth embodiment will be described with the same configuration as that of the carbon dioxide immobilizer 700 shown in Fig.

In Example 4, methanol is produced by two-step enzymatic reaction using F _ate DH and MDH in the same manner as in Example 2.

As the mediator and fuel extractant of Example 4, the same one as used in Example 2 is used.

A mixed solution (? _PIL = AIL / PIL = 0.7) of [C ₈ mIm ⁺ ] [TFSA ^- ] and [C ₈ ImH ⁺ ] [TFSA ^- ] which are ionic liquids was used for the nonaqueous phase of Example 4. To this mixed solution, AOT was added and stirred for 20 hours to disperse AOT (0.07M). Subsequently, by a solvent can be added to the lean buffer [0.1M phosphate buffer, pH = 7.0] containing F DH and _ate as MDH enzyme and stirring for 1 hour, [C ₈ mIm ^+] as a non-aqueous phase [TFSA ^-] And [C ₈ ImH ⁺ ] [TFSA ^- ] in the mixed solution of [C ₈ ImH ⁺ ] [TFSA ^- ] and forming a reversed micelle containing water pool.

F _ate DH and MDH as solubilizing enzymes are solubilized in the reverse micelle water pool thus obtained. In Example 4, this reversed micelle in which F _ate DH and MDH were immobilized was used as an enzyme body.

The non-aqueous phase composed of the thus obtained enzyme / reversed micelle / ionic liquid is used as the non-aqueous phase of Example 4, that is, as the non-aqueous phase 712 of the same batch type carbon dioxide immobilization apparatus as shown in FIG.

And a cathode electrode 715 and an anode electrode 714 are provided in the non-aqueous phase. Although not shown in Fig. 10, in the carbon dioxide immobilization apparatus of the fourth embodiment, a reference electrode is further provided on the non-aqueous solution 712 (not shown).

A separator 741 and a porous support (not shown) are provided between the non-aqueous phase and the aqueous phase containing the fuel extract.

And an extraction liquid inlet 55 communicating with the water phase 713 and an extraction liquid outlet 56 are provided. Although not shown in Fig. 10, the water phase 713 of the carbon dioxide immobilizer of Example 4 contains a stirrer. The extractant is stirred by rotating the stirrer with an external stirrer.

Carbon dioxide is introduced from the gas phase in contact with the non-aqueous phase and participates in the enzyme reaction as a substrate of the enzyme F _ate DH dispersed in the non-aqueous phase. As in Example 2, the formic acid or formate produced by the enzyme reaction catalyzed by F _ate DH is used as a substrate for the enzyme reaction catalyzed by the next enzyme MDH, and methanol is finally produced. Methanol is extracted through the separator 741 and the porous support with the extract contained in the water phase. After the methanol concentration of the extract rises with the reaction time and reaches a predetermined concentration, the extract containing methanol is withdrawn from the extract outlet 56 communicating with the water phase. Then, a new extract liquid is introduced from an extract liquid inlet 55 communicating with the water phase, and the above process is repeated.

The fuel production method of Example 4 is a batch type fuel production method and can produce methanol at a high concentration.

In Example 4, since the enzyme is solubilized in the water pool of reversed micelles, the enzyme can be uniformly dispersed in the reaction system (ionic liquid), so that high enzyme activity and high enzyme catalytic efficiency can be obtained.

By using the carbon dioxide immobilization apparatus of Example 4, methanol was obtained from carbon dioxide at a high fuel conversion efficiency.

(Example 5)

The carbon dioxide immobilizer of Example 5 is a batch carbon dioxide immobilizer as in the apparatus of Example 4, and is a device for producing methanol as a fuel from carbon dioxide.

In Example 5, methanol is produced by a two-step enzyme reaction using F _ate DH and MDH in the same manner as in Example 2. [

As the mediator and fuel extractant of Example 5, the same ones as those of Example 2 are used.

In Example 5, an enzyme / reversed micelle / ionic liquid was prepared in the same manner as in Example 4, and further gelled in the following manner.

Gelatin powder was appropriately added to a mixture (enzyme / reverse micelle / ionic liquid non-aqueous phase) in which an enzyme body containing enzyme / reverse micelle was dispersed, and stirred vigorously at a temperature of 40 ° C to 50 ° C for about 30 minutes. Subsequently, the mixed solution was cooled to 30 DEG C with stirring, and the stirring was continued until the solution became very dense and homogeneous. The resulting suspension was allowed to stand at room temperature until it became a transparent gel.

By the above process, the gelatin enters the water pool of the enzyme body (reverse micelle) and gels there. Further, since an intermolecular network is formed by gelatin gelled in the water pool, the whole mixture (non-aqueous phase) containing the enzyme body gels. Further, by allowing the turbid solution to stand at room temperature, it is possible to further refold the enzymes ( _{Fe ate} DH and MDH) thermally denatured by heating.

In Example 5, since the enzyme is solubilized in the water pool of reversed micelles, the enzyme can be uniformly dispersed in the reaction system (ionic liquid). Also, since the enzyme is uniformly dispersed in the ion gel prepared from the enzyme / reverse micelle / ionic liquid, high enzyme activity and high enzyme catalytic efficiency can be obtained.

By using the carbon dioxide immobilization apparatus of Example 5, methanol was obtained from carbon dioxide at a high fuel conversion efficiency.

(Example 6)

The carbon dioxide immobilizer of Example 6 is a batch carbon dioxide immobilizer as in the apparatus of Example 4, and is a device for producing methanol as a fuel from carbon dioxide.

In Example 6, methanol is produced by an enzymatic reaction in three steps using F _ate DH, F _ald DH, and ADH in the same manner as in Example 1. [

In Example 6, the enzyme Glutamate dehydrogenase (GDH), which reduces NADH oxidase NAD ⁺ , which is a mediator, to NADH, was dispersed in the non-aqueous phase. The enzyme bodies 11 containing these four enzymes were obtained by dispersing and immobilizing silica gel in the same manner as in Example 1 and impregnating 3 mM NADH with a pH7 and 0.1 M phosphate buffer solution. The obtained enzyme body (11) was dispersed in EMIMTFSI which is the medium of the first non-aqueous phase.

The non-aqueous phase of the enzyme body / ionic liquid obtained by the above method was used as the non-aqueous phase 712 shown in Fig.

On the other hand, in Example 6, since the enzyme Glutamate dehydrogenase (GDH) that reduces NAD ⁺ to NADH is further included in the non-aqueous phase 712, the cathode 715 and the anode 714 shown in FIG. 10, The reference electrode can be omitted.

In Example 6, NADH consumed at the time of producing methanol by an enzyme reaction using three enzymes can be rapidly regenerated by the enzyme GDH. Therefore, the configuration of the carbon dioxide immobilization apparatus of Example 6 can prevent the stop of the enzyme reaction due to depletion of NADH, and a high methanol concentration can be obtained.

Glutamic acid necessary for the regeneration reaction of NADH by the enzyme GDH can be supplied from the aqueous phase.

In all of the above-described first to sixth embodiments, since the ionic liquid is used as the absorbing medium for carbon dioxide, the solubility of carbon dioxide is greatly increased. Therefore, the enzyme reaction of Examples 1 to 6 can be used to produce methanol, which is a high concentration fuel.

The carbon dioxide immobilization apparatus according to at least one of the embodiments and examples described above includes a non-aqueous phase and a water phase. The non-aqueous phase includes an ionic liquid, an enzyme body, and a mediator. The enzyme body catalyzes the reduction reaction of carbon dioxide or its reduction product. The mediator acts as a reducing agent or a coenzyme in the reduction reaction. Also, carbon dioxide or a reduction product thereof is supplied to the non-aqueous phase, and a reaction product is produced by the reduction reaction. The water phase contains an extract. In the water phase, the reaction product is supplied from the non-aqueous phase. With this configuration, it is possible to provide a carbon dioxide immobilization apparatus and a fuel production system that fix carbon dioxide with high efficiency.

Although some embodiments of the present invention have been described, these embodiments are presented as examples, and it is not intended to limit the scope of the invention. These new embodiments can be implemented in various other forms, and various omissions, substitutions, and alterations can be made without departing from the gist of the invention. These embodiments and their modifications fall within the scope and spirit of the invention, and are included in the scope of equivalents to the invention described in the claims.

Claims (20)

A non-aqueous phase containing an ionic liquid, an enzyme body catalyzing a reduction reaction of carbon dioxide or a reduction product thereof, and a mediator acting as a reducing agent or a coenzyme in the reduction reaction,
And an extraction liquid containing water, wherein the reaction product comprises a water phase supplied from the non-aqueous phase. The carbon dioxide immobilization apparatus according to claim 1, wherein the non-aqueous phase comprises a first non-aqueous phase which is supplied with carbon dioxide from the gaseous phase to produce a first reaction product by its reduction reaction. The method according to claim 1,
A first non-aqueous phase which is supplied with carbon dioxide and which produces a first reaction product by its reduction reaction,
A second non-aqueous phase which is supplied with the first reaction product to produce a second reaction product by its reduction reaction;
The third reaction product is fed to produce a third reaction product by its reduction reaction.
/ RTI &gt;
The water-
A first water phase to which the first reaction product is supplied from the first non-aqueous phase to supply the first reaction product to the second non-
A second aqueous phase which is supplied with the second reaction product from the second non aqueous phase and supplies the second reaction product to the third non aqueous phase,
And a third water phase from which the third reaction product is supplied from the third non-aqueous phase. The method according to claim 1,
A first non-aqueous phase which is supplied with carbon dioxide and which produces a first reaction product by its reduction reaction,
A second non-aqueous phase to which the first reaction product is supplied from the first non-aqueous phase to produce a second reaction product by its reduction reaction;
And a third non-aqueous solution containing the second non-aqueous phase, wherein the second reaction product is supplied from the second non-aqueous phase,
/ RTI &gt;
And the third reaction product is supplied to the water phase from the third non-aqueous phase. The carbon dioxide immobilization apparatus according to claim 3 or 4, wherein carbon dioxide is supplied from the gas phase to the first non-aqueous phase. The carbon dioxide immobilization apparatus according to any one of claims 2 to 4, wherein carbon dioxide is supplied from the atmosphere to the first non-aqueous phase. The carbon dioxide immobilization apparatus according to any one of claims 1 to 4, further comprising a separator provided between the non-aqueous phase and the aqueous phase, the separator including a permeation-separating membrane. The carbon dioxide immobilization apparatus according to any one of claims 1 to 4, wherein the water phase further comprises a proton source for supplying a proton to the non-water phase. 5. The method according to any one of claims 1 to 4, wherein at least one of the enzyme bodies comprises a first complex comprising a molecular assembly comprising an enzyme, an enzyme and a dispersing agent, a core portion comprising an enzyme, A second complex comprising a microcapsule having a shell part, a cell including an enzyme, a microorganism including an enzyme, and an enzyme and a support immobilized thereon. The carbon dioxide immobilization apparatus according to any one of claims 1 to 4, further comprising an external flow path through which the water phase flows. The carbon dioxide immobilization apparatus according to any one of claims 1 to 4, wherein each of the plurality of single cells includes the non-aqueous phase and the aqueous phase, and the plurality of single cells are laminated to form a stacked structure . The carbon dioxide immobilization apparatus according to any one of claims 1 to 4, wherein the non-aqueous phase comprises a porous film on which the enzyme substance is dispersed or supported and which is also wound. The method according to claim 12, wherein the wound porous film is wound a plurality of times such that a plurality of layered portions are arranged in a radial direction,
The enzyme body is a plurality of enzyme bodies,
Wherein the plurality of enzyme bodies are dispersed or supported on the plurality of layers so that other enzyme bodies are arranged in the radial direction. The carbon dioxide immobilization apparatus according to any one of claims 1 to 4, further comprising at least one pair of electrodes provided on the non-aqueous phase. 15. The carbon dioxide immobilization apparatus according to claim 14, further comprising a reference electrode provided on the water phase. A fuel cell system comprising: a fuel generating unit including the carbon dioxide immobilization apparatus according to any one of claims 1 to 4;
A carbon dioxide supplying unit for supplying carbon dioxide to the fuel generating unit,
An extractor recovery unit for recovering the reaction product from the fuel generator,
Fuel mixture. A fuel generating section including the carbon dioxide immobilization apparatus according to claim 14;
A carbon dioxide supplying unit for supplying carbon dioxide to the fuel generating unit,
An extraction liquid recovery unit for recovering the reaction product from the fuel generating unit,
A cell voltage control unit for controlling a voltage applied to the pair of electrodes,
Fuel mixture. A fuel generating section including the carbon dioxide immobilization apparatus according to claim 14;
A carbon dioxide supplying unit for supplying carbon dioxide to the fuel generating unit,
An extraction liquid recovery unit for recovering the reaction product from the fuel generating unit,
A current controller for controlling a current flowing between the pair of electrodes,
Fuel mixture. The fuel production system according to claim 16, further comprising a temperature control section for controlling the temperature in the fuel generation section. 17. The fuel production system according to claim 16, wherein the carbon dioxide supply unit has a function of controlling a pressure of a gas containing carbon dioxide to be supplied to the fuel generation unit.

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