JP2019183286A - Organic matter production method and organic matter production system - Google Patents

Abstract

To provide an organic matter production method and organic matter production system that make it possible to efficiently produce organic matter under a low-temperature environment.SOLUTION: When an aqueous solution comprising carbon dioxide is electrolyzed to produce organic matter, a pH of the aqueous solution at the time of electrolysis is controlled in the range of 5-10.SELECTED DRAWING: Figure 7

Description

  The present invention relates to an organic substance generation method and an organic substance generation system for generating an organic substance from carbon dioxide.

  In recent years, there is concern about the impact on global warming due to an increase in carbon dioxide in the atmosphere, and there is a demand for suppression of carbon dioxide emissions.

  For example, the fuel production apparatus disclosed in Patent Document 1 adjusts the flow rate so that water vapor and carbon dioxide have a predetermined molar ratio, and then the water vapor and carbon dioxide are supplied to the anode and cathode electrodes to which electric power is applied. It is supplied to the cathode electrode side and electrolyzed. And after cooling and pressurizing hydrogen and carbon monoxide produced | generated by this electrolysis, a fuel is synthesize | combined through a catalyst. In this fuel production apparatus, steam and carbon dioxide are heated to a high temperature to promote electrolysis, thereby improving the efficiency of fuel synthesis and suppressing the amount of carbon dioxide emission.

JP 2013-119556 A

  However, in the above fuel production apparatus, water vapor and carbon dioxide are heated to a high temperature of 600 ° C. to 1100 ° C. in order to promote electrolysis, so that the apparatus configuration is complicated to realize such a high temperature environment. In addition to this, there is a problem that the amount of energy used other than electrolysis becomes large.

  The present invention aims to solve this problem. That is, an object of the present invention is to provide an organic substance generation method and an organic substance generation system capable of efficiently generating an organic substance even in a low temperature environment.

  The inventors of the present invention adopted a method of electrolyzing an aqueous solution containing carbon dioxide to produce an organic substance, and repeatedly conducted intensive tests focusing on the pH of the aqueous solution in this method. The inventors have found that organic substances can be efficiently generated when the pH of the aqueous solution falls within a specific range, and have reached the present invention.

  The invention described in claim 1 is a method for producing an organic substance by electrolyzing an aqueous solution containing carbon dioxide, in order to solve the above-mentioned problem, wherein the pH of the aqueous solution during the electrolysis is adjusted. It is an organic substance production | generation method characterized by controlling in the range of 5-10.

  The invention described in claim 2 is the invention described in claim 1, wherein an aqueous solution generating step of generating carbon dioxide in water in the generation container to generate the aqueous solution, and the aqueous solution in the generation container A moving step of moving the aqueous solution from the electrolytic solution to a separate electrolysis vessel, and an electrolysis step of electrolyzing the aqueous solution in the electrolysis vessel, wherein the pH of the aqueous solution is within the range of 5 to 10 in the production vessel It is characterized by controlling to.

  The invention described in claim 3 is the invention described in claim 2, characterized in that, in the electrolysis step, the aqueous solution in the electrolysis vessel is caused to flow.

  The invention described in claim 4 is the invention described in any one of claims 1 to 3, wherein the pH of the aqueous solution during the electrolysis is adjusted to 5 to 10 by adding a base to the aqueous solution. It is characterized by controlling within the range.

  In order to achieve the above object, the invention described in claim 5 is an aqueous solution generator that generates an aqueous solution containing carbon dioxide, and an electrolyzer that electrolyzes the aqueous solution generated by the aqueous solution generator. And a pH control unit that controls the pH of the aqueous solution during the electrolysis within a range of 5 to 10.

  The invention described in claim 6 is the invention described in claim 5, wherein the aqueous solution generation unit has a generation container in which the aqueous solution is generated by absorbing carbon dioxide into water therein, The electrolysis unit has an electrolysis vessel separate from the production vessel in which the aqueous solution is electrolyzed, and the pH control unit adjusts the pH of the aqueous solution in the production vessel to 5 to 10 And moving means for moving the aqueous solution from the production vessel to the electrolysis vessel.

  The invention described in claim 7 is the invention described in claim 6, further comprising a flow means for flowing the aqueous solution in the electrolysis vessel.

  The invention described in claim 8 is the invention described in claim 7, wherein the electrolysis section includes a plurality of anodes and a plurality of cathodes arranged alternately in the electrolysis container, and the electrolysis A plurality of diaphragms that divide the container into a plurality of accommodating portions that individually accommodate the plurality of anodes and the plurality of cathodes, respectively, and the aqueous solution is divided into the plurality of accommodating portions in one direction. It is configured to be discharged from the electrolysis container immediately after flowing and passing.

  The invention described in claim 9 is the invention described in claim 7, wherein the electrolysis section includes a plurality of anodes and a plurality of cathodes arranged alternately in the electrolysis container, and the electrolysis A plurality of diaphragms for partitioning a plurality of anodes and a plurality of cathodes into a plurality of accommodating portions, respectively, and the aqueous solution is a plurality of the plurality of accommodating portions. Another electrolyte aqueous solution that flows in one direction only within the accommodating portion in which the cathode is accommodated, is discharged from the electrolysis vessel immediately after passing through the accommodating portion, and is isolated from the aqueous solution, is contained in the plurality of accommodating portions. It is configured to flow in one direction only within the housing portion in which the plurality of anodes are housed, and to be discharged from the electrolysis container immediately after passing through the housing portion. is there.

  The invention described in claim 10 is the invention described in claim 8 or 9, wherein the plurality of anodes and the plurality of cathodes are formed in a plate shape and are arranged in parallel, Among the plurality of anodes and the plurality of cathodes, adjacent anodes and cathodes form a set, and the inter-electrode space distance of the anode and the cathode forming the set is 2.5 mm or less. To do.

  The invention described in claim 11 is the invention described in claim 10, wherein at least one of the plurality of anodes and the plurality of cathodes is provided with one or a plurality of openings. It is characterized by being.

  The invention described in claim 12 is the invention described in any one of claims 5 to 11, wherein the pH control unit adds the base to the aqueous solution, thereby the aqueous solution at the time of the electrolysis. The pH is controlled within the range of 5-10.

  The invention described in claim 13 is the invention described in any one of claims 5 to 12, further comprising an organic substance extraction unit for extracting an organic substance, wherein the organic substance extraction part is an electric power generated by the electrolysis unit. It has at least one of gas organic substance extraction means for extracting organic substances contained in the gas generated by decomposition and liquid organic substance extraction means for extracting organic substances contained in the aqueous solution after being electrolyzed by the electrolysis section. It is characterized by that.

  In the invention described in claim 14, in the invention described in claim 13, the organic matter extraction part has the liquid organic matter extraction means, and the aqueous solution after the organic matter is extracted by the liquid organic matter extraction means. Is further provided with a liquid feeding means for sending the solution to the aqueous solution generation unit.

  According to the first aspect of the present invention, the pH in the electrolysis in the aqueous solution containing carbon dioxide is controlled within the range of 5-10. Since it did in this way, the equilibrium state of aqueous solution inclines in the direction used as a state in which more hydrogencarbonate ion exists, Therefore, more organic substance is produced | generated by electrolyzing more hydrogencarbonate ion. Therefore, organic substances can be efficiently generated even in a low temperature environment.

  According to the invention described in claim 2, an aqueous solution containing carbon dioxide is produced by absorbing carbon dioxide in water in the production container, and the produced aqueous solution is separated from the production container. And the moved aqueous solution is electrolyzed in an electrolysis container. Further, the pH of the aqueous solution is controlled within the range of 5 to 10 in the production container. Since it did in this way, since the aqueous solution is moved from the production container for controlling its pH to a separate electrolysis container, for example, compared with the case where the production and electrolysis of the aqueous solution are performed simultaneously in one container, When controlling the pH, it is not affected by the change in pH due to electrolysis, and therefore, it is possible to suppress a decrease in the accuracy of controlling the pH of the solution. Therefore, organic substances can be generated more efficiently even in a low temperature environment.

  According to the third aspect of the present invention, the aqueous solution in the electrolysis vessel is caused to flow in the electrolysis process in which electrolysis is performed. Since it did in this way, the bubble which arises on the surface of an electrode by electrolysis flows away by the flow of aqueous solution, Therefore The increase in the electrical resistance by the said bubble can be suppressed. Therefore, organic substances can be generated more efficiently even in a low temperature environment.

  According to the invention described in claim 4, the pH of the aqueous solution at the time of electrolysis is controlled within a range of 5 to 10 by adding a base to an aqueous solution containing carbon dioxide or water as a solvent thereof. . Since it did in this way, compared with the case where pH is controlled by the quantity (namely, density | concentration) which contains carbon dioxide, for example, pH of aqueous solution can be controlled easily and accurately by adjusting the addition amount of a base. Can do. Therefore, organic substances can be generated more efficiently even in a low temperature environment.

  According to the invention described in claim 5, an aqueous solution generation unit that generates an aqueous solution containing carbon dioxide, an electrolysis unit that electrolyzes the aqueous solution generated by the aqueous solution generation unit, and electrolysis by the electrolysis unit A pH controller for controlling the pH of the aqueous solution in the range of 5 to 10. As a result, the equilibrium state of the aqueous solution is tilted in a direction in which more hydrogen carbonate ions are present due to the control of the pH control unit, so that more hydrogen carbonate ions are electrolyzed. A lot of organic matter is produced. Therefore, organic substances can be efficiently generated even in a low temperature environment.

  According to the invention described in claim 6, the aqueous solution generation unit includes a generation container in which an aqueous solution containing carbon dioxide is generated by absorbing carbon dioxide into water, and the electrolysis unit includes: The electrolysis solution is electrolyzed inside and the electrolysis vessel is provided separately from the production vessel, and the pH controller controls the pH of the aqueous solution within the range of 5 to 10 in the production vessel. And the moving means which moves aqueous solution from the container for production | generation to the container for electrolysis is further provided. Since it did in this way, since the aqueous solution is moved from the production vessel for controlling its pH to a separate electrolysis vessel, for example, compared with the case where the production of the aqueous solution and the electrolysis are performed simultaneously in one vessel, the pH When controlling the pH, it is not affected by the change in pH due to electrolysis, and therefore, it is possible to suppress a decrease in the accuracy of pH control of the solution. Therefore, organic substances can be generated more efficiently even in a low temperature environment.

  According to the seventh aspect of the present invention, it is further provided with fluid means for fluidizing the aqueous solution in the electrolysis container. Since it did in this way, the bubble which arises on the surface of an electrode by electrolysis flows away by the flow of aqueous solution, Therefore The increase in the electrical resistance by the said bubble can be suppressed. Therefore, organic substances can be generated more efficiently even in a low temperature environment.

  According to the eighth aspect of the present invention, the aqueous solution containing carbon dioxide is divided into a plurality of accommodating portions that individually accommodate the plurality of anodes and the plurality of cathodes, and the inside of each accommodating portion is unidirectional. Immediately after flowing and passing, the electrolysis container is discharged. Thus, the aqueous solution on the anode side after the electrolysis contains oxygen generated on the surface of the anode by the electrolysis, and this oxygen can be prevented from coming into contact with the anode again. Since the cathode and the cathode are separated by a diaphragm, it is possible to prevent this oxygen from coming into contact with the cathode. Therefore, it is possible to suppress deterioration of the electrode due to contact with oxygen. Therefore, organic substances can be generated more efficiently even in a low temperature environment.

  According to the ninth aspect of the present invention, the aqueous solution containing carbon dioxide flows in one direction only in the housing portion in which the plurality of cathodes among the plurality of housing portions are housed, and the housing portion is Immediately after passing, it is discharged from the electrolysis container. Further, another electrolytic aqueous solution isolated from the aqueous solution flows in one direction only in the housing portion in which the plurality of anodes are housed among the plurality of housing portions, and immediately after passing through the housing portion, the electrolysis container Discharged from. Thus, the aqueous solution on the anode side after the electrolysis contains oxygen generated on the surface of the anode by the electrolysis, and this oxygen can be prevented from coming into contact with the anode again. Since the cathode and the cathode are separated by a diaphragm, it is possible to prevent this oxygen from coming into contact with the cathode. Further, in a configuration in which the aqueous solution after electrolysis is reused, oxygen generated by electrolysis may be dissolved in such a reused aqueous solution. Isolation can prevent dissolved oxygen from coming into contact with the cathode. Therefore, it is possible to suppress deterioration of the electrode due to contact with oxygen. Therefore, organic substances can be generated more efficiently even in a low temperature environment.

  According to the invention described in claim 10, the plurality of anodes and the plurality of cathodes are formed in a flat plate shape, and are arranged in parallel, and the anodes adjacent to each other among the plurality of anodes and the plurality of cathodes. Each of the cathode and cathode constitutes a set, and the space between the electrodes of the anode and the cathode constituting the set is 2.5 mm or less. As a result, in the electrolysis, the narrower the gap between the electrodes, the better the efficiency. On the other hand, the aqueous solution is less likely to flow between the electrodes, and the removal of bubbles on the electrode surface is hindered to maintain good efficiency. However, by setting the intervals between the plurality of anodes and the plurality of cathodes within the above range, the efficiency of electrolysis and the maintenance thereof can be appropriately balanced.

  According to the invention described in claim 11, at least one of the plurality of anodes and the plurality of cathodes is provided with one or a plurality of openings. Since it did in this way, aqueous solution can flow more easily between electrodes, the bubble removal of the electrode surface is accelerated | stimulated, and the efficiency of electrolysis can be maintained more appropriately.

  According to the invention described in claim 12, the pH control unit controls the pH of the aqueous solution during electrolysis within a range of 5 to 10 by adding a base to the aqueous solution or water as a solvent thereof. Since it did in this way, compared with the case where pH is controlled by the quantity (namely, density | concentration) which contains carbon dioxide, for example, pH of aqueous solution can be controlled easily and accurately by adjusting the addition amount of a base. Can do. Therefore, organic substances can be generated more efficiently even in a low temperature environment.

  According to the invention described in claim 13, further comprising an organic matter extraction unit for extracting an organic matter, wherein the organic matter extraction unit extracts an organic matter contained in a gas generated by electrolysis by the electrolysis unit, and It has at least one of the liquid organic substance extraction means which extracts the organic substance contained in the aqueous solution after the electrolysis by the electrolysis part. Since it did in this way, at least one of the gaseous organic substance or water-soluble organic substance which arose by electrolysis can be obtained.

  According to the fourteenth aspect of the present invention, the organic substance extraction unit further includes a liquid organic substance extraction unit, and further includes a liquid feeding unit that sends the aqueous solution after the organic substance is extracted by the liquid organic substance extraction unit to the aqueous solution generation unit. ing. Since it did in this way, carbon dioxide can be included again in the aqueous solution after electrolysis, and it can reuse.

It is a schematic block diagram of the organic substance production | generation apparatus of one Embodiment of this invention. It is a figure explaining the structure of the gas absorption part with which the organic substance production | generation apparatus of FIG. 1 is provided. It is a figure explaining the structure of the electrolytic synthesis part with which the organic substance production | generation apparatus of FIG. 1 is equipped, and an organic substance production | generation part. It is a figure explaining arrangement | positioning of the anode of the electrolytic synthesis part of FIG. 2, a cathode, and a diaphragm. It is a figure explaining the structure of the modification of the gas absorption part of FIG. It is a figure explaining the structure of the modification of the electrolytic synthesis part and organic substance production | generation part of FIG. It is a graph which shows an example of the relationship between the hydrogen ion index | exponent of the aqueous solution which produces | generates the organic substance by electrolysis, and total organic carbon amount ratio. It is a graph which shows an example of the relationship between the distance (space distance between electrodes) of the anode of an electrode used for the production | generation of the organic substance by electrolysis, and the total organic carbon amount ratio. It is a graph which shows an example of the relationship between the aperture ratio of the electrode used for the production | generation of the organic substance by electrolysis, and the total organic carbon amount ratio. It is a graph which shows an example of the relationship between the flow rate of the aqueous solution which flows through the inside of the electrolysis layer which performs electrolysis, and the total organic carbon amount ratio.

  Hereinafter, the organic substance production | generation apparatus of one Embodiment of this invention is demonstrated with reference to FIGS.

  FIG. 1 is a schematic configuration diagram of an organic matter generating apparatus according to an embodiment of the present invention. FIG. 2 is a diagram illustrating a configuration of a gas absorption unit provided in the organic matter generation device of FIG. FIG. 3 is a diagram illustrating the configurations of the electrolytic synthesis unit and the organic matter generation unit provided in the organic matter generation device of FIG. 1. FIG. 4 is a diagram for explaining the arrangement of the anode, the cathode, and the diaphragm of the electrolytic synthesis unit of FIG.

The organic substance generating apparatus of this embodiment electrolyzes an aqueous solution in which carbon dioxide (CO ₂ ) is absorbed in water (H ₂ O), extracts gaseous organic substances from the gas generated by the electrolysis, and after electrolysis A water-soluble organic substance is extracted from the aqueous solution. Examples of organic substances to be extracted include methane (CH ₄ ), ethane (C ₂ H ₆ ), ethylene (C ₂ H ₄ ), methanol (CH ₄ O), ethanol (C ₂ H ₆ O), propanol (C ₃ H ₈ O), formaldehyde (CH ₂ O) and formic acid (CH ₂ O ₂ ). Of course, these are only examples, and organic substances other than these can be generated by adjusting various conditions.

  As shown in FIG. 1, the organic substance production | generation apparatus 1 of this embodiment is the gas absorption part 10 as an aqueous solution production | generation part, the electrolytic synthesis part 20 as an electrolysis part, the organic substance extraction part 30, and a liquid sending means. A treated aqueous solution recovery unit 40 and a control unit 50 as a pH control unit are provided.

  The gas absorption unit 10 generates an aqueous solution in which carbon dioxide is absorbed in water. Moreover, in the gas absorption part 10, it controls so that pH of the produced | generated aqueous solution may be contained in a specific range. As shown in FIG. 2, the gas absorption unit 10 includes a gas absorption tank 11 as a generation container, a pH measurement pipe 12, a pH measurement pump 13, a pH meter 14, and a pH adjustment drug tank 15. The medicine injection pump 16, the transfer pipe 17, and the transfer pump 18 are provided.

  The gas absorption tank 11 is a container that generates an aqueous solution in which carbon dioxide has been absorbed. A pipe (not shown) for supplying gaseous carbon dioxide from the outside to the gas phase section and a pipe (not shown) for discharging excess carbon dioxide from the gas phase section are connected to the gas absorption tank 11. A sprayer 11 a is provided inside the ceiling wall of the gas absorption tank 11. The gas absorption tank 11 is provided with a temperature control device (not shown) so that the temperature of the aqueous solution inside can be adjusted.

  One end of the pH measurement pipe 12 is connected to the liquid phase part of the gas absorption tank 11, and the other end is connected to the sprayer 11a. The pH measurement pipe 12 is connected so that a treated aqueous solution pipe 41 of a treated aqueous solution recovery unit 40 described later joins. In addition, a pipe (not shown) for supplying water from the outside is connected to the pH measurement pipe 12 so as to join.

  The pH measurement pump 13 causes the aqueous solution that is the liquid phase part of the gas absorption tank 11 to flow from one end of the pH measurement pipe 12 toward the other end. Thereby, the aqueous solution that has flowed to the other end of the pH measurement pipe 12 is sprayed from the sprayer 11a into the gas phase portion, and the mist-like aqueous solution falls to the liquid phase portion while absorbing carbon dioxide.

  The pH meter 14 measures the pH of the aqueous solution flowing through the pH measurement pipe 12. The pH meter 14 is connected to a control unit 50 described later, and transmits a signal corresponding to the measured pH to the control unit 50.

The pH adjusting chemical tank 15 contains a base which is a chemical used for controlling the pH of the aqueous solution in the gas absorption tank 11. This agent is, for example, lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na ₂ CO ₃ ), potassium carbonate (K ₂ CO ₃ ), lithium carbonate (LiHCO ₃ ). ), Sodium hydrogen carbonate (NaHCO ₃ ), potassium hydrogen carbonate (KHCO ₃ ), potassium sulfate (K ₂ SO ₄ ) and sulfuric acid (H ₂ SO ₄ ). Of course, these are merely examples, and other substances may be used as long as they act as a base when introduced into an aqueous solution, as long as they do not contradict the purpose of the present invention. The chemical tank 15 for pH adjustment is connected to the treated aqueous solution pipe 41, and the chemical contained in the chemical tank 15 for pH adjustment is introduced into the aqueous solution flowing in the treated aqueous solution pipe 41 by the chemical injection pump 16. The The aqueous solution in which the medicine is charged is sprayed from the sprayer 11a, and the pH of the aqueous solution in the gas absorption tank 11 is adjusted. The medicine injection pump 16 is connected to the control unit 50 and operates based on a control signal from the control unit 50.

  One end of the transfer pipe 17 is connected to the liquid phase part of the gas absorption tank 11, and the other end is connected to the electrolytic synthesis part 20 described later. The transfer pump 18 causes the aqueous solution that is the liquid phase part of the gas absorption tank 11 to flow from one end of the transfer pipe 17 toward the other end. Thereby, the aqueous solution in the gas absorption tank 11 is moved to the electrolytic synthesis unit 20 through the transfer pipe 17. The transfer pipe 17 and the transfer pump 18 constitute a moving unit that moves the aqueous solution from the gas absorption unit 10 to the electrolytic synthesis unit 20. The transfer pump 18 is connected to the control unit 50 and operates based on a control signal from the control unit 50.

  The electrolytic synthesis unit 20 electrolyzes the aqueous solution in which carbon dioxide is absorbed. As shown in FIG. 3, the electrolytic synthesis unit 20 includes an electrolysis tank 21 as an electrolysis vessel, a plurality of anodes 22, a plurality of cathodes 23, a plurality of diaphragms 24, an anode-side discharge pipe 26, a cathode Side discharge pipe 27.

  The electrolysis tank 21 is a container in which an aqueous solution is moved from the gas absorption tank 11 and the aqueous solution is electrolyzed therein. In the electrolysis tank 21, a plurality of anodes 22, a plurality of cathodes 23, and a plurality of diaphragms 24 are arranged in a predetermined order. Specifically, as shown in FIG. 4, an anode 22 and a cathode 23 are arranged to face each other and a diaphragm 24 is arranged between them to form a set of electrode sets S. A plurality (S [1] to S [n]) are arranged in the direction (left-right direction in FIG. 4). Moreover, the diaphragm 24 which is not contained in these is arrange | positioned between each electrode set S [1] -S [n], and also in the arrangement direction both ends of each electrode set S [1] -S [n]. A part of the electrolysis layer 21 is arranged as a partition wall 21a.

Each of the plurality of anodes 22 is connected to a positive electrode of a power supply device (not shown), and each of the plurality of cathodes 23 is connected to a negative electrode of a power supply device (not shown), and between the plurality of anodes 22 and the plurality of cathodes 23. Is applied with a voltage suitable for electrolysis of an aqueous solution (for example, a voltage at which the current density is 800 mA / cm ² or less and the reaction temperature in the electrolysis tank 21 is in the range of 20 ° C. to 80 ° C.). ing. This power supply device outputs a desired voltage and current and obtains electric power from a commercial power supply. In addition to this, natural energy such as sunlight, solar heat, hydraulic power, wind power, geothermal heat, wave power, etc. You may use the power supply device utilized, power supply devices, such as a fuel cell.

  The base materials of the plurality of anodes 22 and the plurality of cathodes 23 are, for example, metal materials such as nickel (Ni), gold (Au), platinum (Pt), copper (Cu), iron (Fe), lead (Pb), It is composed of carbon (C) or conductive ceramic. Of course, these are examples, and other materials than those described above may be used as long as they do not contradict the purpose of the present invention as long as they are suitable materials for an electrode for electrolysis.

  Each of the plurality of cathodes 23 is made of a material widely known as a carbon dioxide reduction catalyst, such as a group 4 element such as titanium (Ti), a group 8 element such as ruthenium (Ru), copper (Cu), or the like. It carries a Group 12 element metal material, an oxide having these metals, a metal complex having these metals and a polypyridine compound or a polypyrrole compound, or a semiconductor material such as GaP. Or the some cathode 23 may be comprised only with the said base material, without carrying | supporting these materials.

  The plurality of anodes 22 and the plurality of cathodes 23 are each formed in a rectangular flat plate shape, and are arranged in parallel to each other. Further, as described above, the plurality of anodes 22 and the plurality of cathodes 23 form a set of adjacent anodes 22 and cathodes 23 with the partition wall 24 interposed therebetween. The inter-electrode space distance between the anode 22 and the cathode 23 included in one set of electrodes S is not a problem as long as the lower limit is 0 mm or more, but is preferably 0.5 mm or more, and the upper limit is 2.5 mm. It is below, and it is preferable that it is 2 mm or less. That is, the inter-electrode spatial distance is set to be included in a range of 0 mm to 2.5 mm, and preferably the inter-electrode spatial distance is set to be included in a range of 0.5 mm to 2 mm. . Here, the inter-electrode space distance is the distance between the anode 22 and the cathode 23 minus the thickness of the diaphragm 24, and the distance a between the anode 22 and the diaphragm 24 and the distance between the cathode 23 and the diaphragm 24. And the distance b are added together (FIG. 4). For example, the inter-electrode space distance of 0 mm means that the anode 22 and the cathode 23 are in contact with the diaphragm 24 between them. If the inter-electrode spatial distance is too wide, the applied voltage must be increased. If the inter-electrode spatial distance is too small, the aqueous solution is difficult to flow and is generated on the surface of the electrodes (ie, the anode 22 and the cathode 23) by electrolysis. Since the air bubbles stay on the surface and the electrical resistance increases, setting them within the above range can appropriately balance them.

  Each of the plurality of anodes 22 and the plurality of cathodes 23 is provided with a plurality of openings arranged uniformly (mesh) throughout. Alternatively, one or several relatively large openings may be provided. The opening is formed in, for example, a circle, a polygon, a star, or the like. As described above, by providing openings in each of the anode 22 and the cathode 23, the aqueous solution easily flows around the anode 22 and the cathode 23. In order to express that a plurality of openings are provided in the anode 22 and the cathode 23 in the enlarged circle of FIG. 4, these are shown in broken lines.

  Further, the openings are provided so that the ratio of the total opening area to the projected external area of the plurality of anodes 22 and the plurality of cathodes 23 (that is, the opening ratio) is included in the range of 10% to 70%, preferably The opening is provided so that the opening ratio is included in the range of 20% to 60%. This is because if the aperture ratio is too low, the effect of the aperture is not exhibited, and if the aperture ratio is too high, the electrode surface area becomes small and the efficiency of electrolysis decreases, so that these are appropriately balanced.

  Moreover, the diaphragm 24 included in each electrode set S [1] to S [n] and the diaphragm 24 not included are disposed in the electrolysis tank 21. In other words, the plurality of diaphragms 24 are electrolyzed. The tank 21 is partitioned into a plurality of accommodating portions 25 that individually accommodate a plurality of anodes 22 and a plurality of cathodes 23. That is, the diaphragm 24 is disposed between the adjacent anode 22 and the cathode 23, and the anode 22 and the cathode 23 are isolated by the diaphragm 24. The plurality of diaphragms 24 are composed of, for example, a film having a film thickness of about 0.05 mm to 0.2 mm and subjected to a surface treatment mainly including a material such as polyethylene or polypropylene and imparting ion exchange characteristics. Has been. Further, the distance between adjacent diaphragms 24 (that is, the diaphragm 24 included in the electrode set S and the diaphragm 24 not included) is about several centimeters.

  Each of the plurality of accommodating portions 25 partitioned by the plurality of diaphragms 24 is connected to the other end of a transfer pipe 17 that is branched into a plurality of branches. In addition, each of the housing portions 25 in which the anodes 22 are housed (hereinafter referred to as “anode housing portions 25”) among the plurality of housing portions 25 is divided into a plurality of anode side discharge pipes 26 corresponding to them. Is connected so as to face the other end of the transfer pipe 17 with the anode 22 in between. In addition, each of the housing portions 25 in which the cathode 23 is housed (hereinafter referred to as “cathode housing portion 25”) among the plurality of housing portions 25 is provided with a cathode-side discharge pipe 27 that is branched into a plurality of branches. One end is connected so as to face the other end of the transfer pipe 17 across the cathode 23.

  As a result, the aqueous solution that has been flowed through the transfer pipe 17 by the transfer pump 18 flows into the plurality of accommodating portions 25 and flows in these directions in one direction, and then into the anode-side discharge pipe 26 and the cathode-side discharge pipe 27. It flows in and is discharged from the electrolysis tank 21 through these. The other end of the anode side discharge pipe 26 and the other end of the cathode side discharge pipe 27 are connected to the organic substance extraction unit 30.

  The flow rate of the aqueous solution flowing in the plurality of accommodating portions 25, that is, the flow rate of the aqueous solution flowing on the surfaces of the plurality of anodes 22 and the plurality of cathodes 23 is included in a specific range by the transfer pump 18 of the gas absorption unit 10. To be adjusted. The transfer pump 18 corresponds to a flow means. Of course, it is not limited to this, For example, you may provide the flow means which flows aqueous solution in the electrolysis tank 21. FIG.

  The organic substance extraction unit 30 extracts organic substances contained in the aqueous solution after electrolysis. The organic matter extraction unit 30 includes a gaseous organic matter extraction unit 31 and a liquid organic matter extraction unit 32.

  The gaseous organic matter extraction unit 31 extracts gaseous organic matter contained in the aqueous solution after electrolysis and gas generated by electrolysis contained in the aqueous solution. The gaseous organic matter extraction unit 31 includes an anode-side extraction tank 31a to which the other end of the anode-side discharge pipe 26 is connected, and a cathode-side extraction tank 31b to which the other end of the cathode-side discharge pipe 27 is connected. .

The anode-side extraction tank 31a is composed of a gas-liquid separation drum that separates and recovers oxygen (O ₂ ) generated when passing through the anode housing portion 25. The anode-side extraction tank 31a can make it easier to recover oxygen (O ₂ ) generated by slightly reducing the pressure in the system.

Similarly to the anode side extraction tank 31a, the cathode side extraction tank 31b is also composed of a gas-liquid separation drum, and includes gaseous organic substances such as methane, ethane, ethylene and formaldehyde contained in the aqueous solution that has passed through the cathode housing portion 25, hydrogen ( H ₂ ), carbon monoxide (CO) is extracted. The mixed gas separated and recovered is purified by combining the adsorbent, the separation membrane and the like by appropriately changing the pressure and temperature conditions according to the composition.

  The aqueous solution extracted in the anode side extraction tank 31 a and the cathode side extraction tank 31 b is moved to the liquid organic matter extraction unit 32 through the pipe 33.

  The liquid organic matter extraction unit 32 has a distillation column 32a. The aqueous solution is transferred from the gaseous organic matter extraction unit 31 to the distillation column 32a through the pipe 33, and in the distillation column 32a, water-soluble water that is liquid at normal temperature and normal pressure, such as methanol, ethanol, and propanol, and becomes gas at less than 100 ° C. The organic matter is extracted by distillation. The distillation tower 32a is configured to perform distillation using steam using a heat source such as a boiler. For example, a heat medium such as a molten salt heated by solar heat is used as a heat storage material, and is generated using the heat storage material. The structure etc. which perform distillation using a vapor | steam may be sufficient.

  The treated aqueous solution recovery unit 40 sends a part of the aqueous solution extracted by the organic substance extraction unit 30 back to the gas absorption unit 10. The treated aqueous solution recovery unit 40 includes a processed aqueous solution pipe 41 and a recovery pump 42.

  One end of the treated aqueous solution pipe 41 is connected to the distillation column 32 a and the other end is connected to the pH measurement pipe 12. The recovery pump 42 causes the aqueous solution in the distillation column 32 a to flow from one end of the treated aqueous solution pipe 41 toward the other end. Thereby, the aqueous solution in the distillation column 32a is moved to the gas absorption part 10 through the processed aqueous solution piping 41. The aqueous solution moved to the gas absorption unit 10 (specifically, the pH measurement pipe 12) merges with the aqueous solution flowing in the pH measurement pipe 12, and is brought into the gas phase part of the gas absorption tank 11 by the sprayer 11a. Sprayed. The treated aqueous solution pipe 41 is branched on the way, and the remaining part of the aqueous solution is discharged from the branch.

  The control unit 50 is constituted by, for example, a microcomputer with a built-in CPU, ROM, RAM, and the like, and controls the entire organic matter generating apparatus 1.

  The control unit 50 is connected to the pH meter 14 and the medicine injection pump 16. The control unit 50 acquires the pH of the aqueous solution in the gas absorption tank 11 based on the signal transmitted from the pH meter 14, and transmits a control signal to the drug injection pump 16 based on the acquired pH to absorb the gas. The medicine in the pH adjustment medicine tank 15 is introduced into the treated aqueous solution pipe 41 by the medicine injection pump 16 so that the pH of the aqueous solution in the tank 11 is within a specific range.

  The control unit 50 controls the pH of the aqueous solution in the gas absorption tank 11 to be included in the range of 5-10. Alternatively, by adding a drug, the pH is controlled to be included in the range of 5 to 10, preferably the pH is controlled to be included in the range of 6.8 to 9.9, and more preferably Is controlled so that the pH falls within the range of 7.2 to 9.5.

  In addition, the transfer pump 18 is connected to the control unit 50. The control unit 50 transmits a control signal to the transfer pump 18 to move the aqueous solution from the gas absorption tank 11 to the electrolysis tank 21, and the flow rate of the aqueous solution flowing in the plurality of accommodating portions 25 of the electrolysis tank 21. Control.

  The controller 50 controls the flow rate of the aqueous solution flowing in the plurality of accommodating portions 25 to be included in the range of 0.01 m / min to 11 m / min, and preferably the flow rate is 2 m / min to 10 m / min. It is controlled so as to be included in the range of minutes, and more preferably, the flow rate is controlled to be included in the range of 4 m / min to 9 m / min.

  The control unit 50 is connected to the pH measurement pump 13, the recovery pump 42, a power supply device (not shown), and the like, and the control unit 50 also transmits control signals to these to control the operation. The control unit 50 also controls the supply of water and carbon dioxide to the gas absorption unit 10.

  Next, an example of the organic matter generating operation in the organic matter generating apparatus 1 described above will be described.

The organic substance generating apparatus 1 supplies carbon dioxide to a gas phase part from a pipe (not shown) connected to the gas absorption tank 11. Then, water is supplied from a pipe (not shown) connected to the pH measurement pipe 12 and sprayed into the gas absorption tank 11 by the sprayer 11a. Thereby, the mist-like water falls while absorbing carbon dioxide, and an aqueous solution in which carbon dioxide is absorbed by water is generated in the gas absorption tank 11 (aqueous solution generation step). In general, the carbon dioxide absorbed in water undergoes an equilibrium reaction represented by the following formula depending on the pH of the absorbed liquid.
CO ₂ + H ₂ O⇔H ₂ CO ₃ (1)
^{_{H 2 CO 3 ⇔ H + +}} HCO 3 - ··· (2)
HCO _3- ⇔ H ⁺ + CO ₃ ^2- (3)

  Next, when a predetermined amount of the aqueous solution in the gas absorption tank 11 is stored, the organic matter generating device 1 operates the transfer pump 18 to continuously move the aqueous solution from the gas absorption tank 11 to the electrolysis tank 21 through the transfer pipe 17. (Transfer process). The aqueous solution that has moved to the electrolysis tank 21 flows in the plurality of accommodating portions 25 in one direction. At this time, the transfer pump 18 is controlled so that the flow rate of the aqueous solution in the plurality of accommodating portions 25 is included in a specific range.

  Next, the organic matter generating device 1 applies a voltage between the plurality of anodes 22 and the plurality of cathodes by a power supply device (not shown). Thereby, the aqueous solution in the some accommodating part 25 is electrolyzed and an organic substance is produced | generated (electrolysis process). The aqueous solution after being electrolyzed in the plurality of accommodating portions 25 is moved to the organic substance extraction unit 30 through the anode side discharge pipe 26 and the cathode side discharge pipe 27.

  Next, the organic matter generating apparatus 1 extracts a gas such as gaseous organic matter from the aqueous solution moved to the organic matter extraction unit 30 in the anode-side extraction tank 31a and the cathode-side extraction tank 31b of the gaseous organic matter extraction unit 31, and then the liquid Water-soluble organic substances are extracted in the distillation column 32a of the organic substance extraction unit 32 (extraction process).

  Next, the organic matter generating apparatus 1 operates the recovery pump 42 so that a part of the treated aqueous solution from which the organic matter has been extracted is continuously moved to the gas absorption unit 10 through the treated aqueous solution pipe 41 (aqueous solution recovery). Process). As a result, the aqueous solution sent back to the gas absorption unit 10 joins the pH measurement pipe 12 and is sprayed from the sprayer 11a to the gas phase part of the gas absorption tank 11 to become an aqueous solution in which carbon dioxide is absorbed again. Further, the organic matter generating device 1 discharges the remaining part of the aqueous solution from the treated aqueous solution pipe 41.

  As described above, the organic matter generating apparatus 1 circulates the aqueous solution containing carbon dioxide by continuously executing the above operation so as to sequentially flow through the gas absorption unit 10, the electrolytic synthesis unit 20, and the organic matter extraction unit 30. Then, the generation of the aqueous solution, the electrolysis and the extraction of the organic matter are continuously performed.

Moreover, the organic substance production | generation apparatus 1 operates the pH measurement pump 13 in parallel with the said circulation operation | movement, and makes the aqueous solution in the gas absorption tank 11 flow in the piping 12 for pH measurement. Then, the pH of the aqueous solution flowing through the pH measurement pipe is measured by the pH meter 14, and the chemical injection pump 16 is operated based on the measured pH, so that the pH of the aqueous solution is included in a specific range. A chemical | medical agent is thrown into the aqueous solution which flows through the inside of the spent aqueous solution piping 41 (pH control process). Thereby, the pH of the aqueous solution in the gas absorption tank 11 is controlled so as to be included in a specific range, and the equilibrium state of the aqueous solution is inclined in a direction in which more bicarbonate ions (HCO ³⁻ ) are present. . This pH-controlled aqueous solution is supplied to the electrolytic synthesis unit 20 by the circulation operation. In other words, the organic matter generating device 1 controls the pH of the aqueous solution during electrolysis in the electrolytic synthesis unit 20 to a specific range.

  As mentioned above, according to this embodiment, pH at the time of electrolyzing in the aqueous solution containing carbon dioxide is controlled in the range of 5-10. Since it did in this way, the equilibrium state of aqueous solution inclines in the direction used as a state in which more hydrogencarbonate ion exists, Therefore, more organic substance is produced | generated by electrolyzing more hydrogencarbonate ion. Therefore, organic substances can be efficiently generated even in a low temperature environment.

  Further, an aqueous solution containing carbon dioxide is generated in the gas absorption tank 11, the generated aqueous solution is moved from the gas absorption tank 11 to a separate electrolysis tank 21, and the moved aqueous solution is transferred in the electrolysis tank 21. Electrolyze. Further, the pH of the aqueous solution is controlled in the gas absorption tank 11. Since it did in this way, since aqueous solution is moved from the gas absorption tank 11 which controls the pH to the separate electrolysis tank 21, compared with the case where the production | generation and electrolysis of aqueous solution are performed simultaneously in one container, for example. Thus, when the pH is controlled, it is not affected by the change in pH due to electrolysis, and therefore it is possible to suppress a decrease in the accuracy of the pH control of the solution. Therefore, organic substances can be generated more efficiently even in a low temperature environment.

  Moreover, the aqueous solution in the some accommodating part 25 of the electrolysis tank 21 is made to flow in the case of electrolysis. As a result, bubbles generated on the surfaces of the electrodes (a plurality of anodes 22 and a plurality of cathodes 23) by electrolysis flow away due to the flow of the aqueous solution, and therefore, an increase in electrical resistance due to the bubbles can be suppressed. it can. Therefore, organic substances can be generated more efficiently even in a low temperature environment.

  In addition, by adding a chemical (base) to the aqueous solution, the pH of the aqueous solution at the time of electrolysis is controlled within the range of 5 to 10, for example, the pH is adjusted depending on the amount (ie, concentration) of carbon dioxide. Compared with the case of controlling, the pH of the aqueous solution can be easily and accurately controlled by adjusting the amount of the drug added. Therefore, organic substances can be generated more efficiently even in a low temperature environment.

  Moreover, the gas absorption part 10 which produces | generates the aqueous solution containing carbon dioxide, the electrolytic synthesis part 20 which electrolyzes the aqueous solution produced | generated by the gas absorption part 10, and pH of the aqueous solution in the case of the electrolysis by an electrolysis part And a control unit 50 for controlling within the range of 5-10. Since it did in this way, by the control of the control part 50, the equilibrium state of aqueous solution inclines in the direction which will be in the state in which more hydrogen carbonate ions exist, Therefore, more hydrogen carbonate ions are electrolyzed. A lot of organic matter is produced. Therefore, organic substances can be efficiently generated even in a low temperature environment.

  Moreover, the gas absorption part 10 has a gas absorption tank 11 in which an aqueous solution containing carbon dioxide is generated, and the electrolytic synthesis part 20 includes a gas absorption tank 11 in which the aqueous solution is electrolyzed. The electrolysis tank 21 is provided separately, and the control unit 50 controls the pH of the aqueous solution in the gas absorption tank 11. And the transfer piping 17 and the transfer pump 18 which move aqueous solution from the gas absorption tank 11 to the electrolysis tank 21 are further provided. Since it did in this way, since aqueous solution is moved from the gas absorption tank 11 which controls the pH to the separate electrolysis tank 21, compared with the case where the production | generation and electrolysis of aqueous solution are performed simultaneously in one container, for example. When the pH is controlled, it is not affected by the change in pH due to electrolysis, so that it is possible to suppress a decrease in the accuracy of pH control of the solution. Therefore, organic substances can be generated more efficiently even in a low temperature environment.

  Further, a transfer pump 18 is provided for flowing the aqueous solution in the plurality of accommodating portions 25 of the electrolysis tank 21. Since it did in this way, the bubble which arises on the surface of an electrode (anode 22 and the cathode 23) by electrolysis flows away by the flow of aqueous solution, Therefore The increase in the electrical resistance by the said bubble can be suppressed. Therefore, organic substances can be generated more efficiently even in a low temperature environment.

  Moreover, the aqueous solution containing carbon dioxide is discharged from the electrolysis tank 21 immediately after flowing in one direction through the plurality of housing portions 25 that individually house the plurality of anodes 22 and the plurality of cathodes 23. . As a result, the aqueous solution on the anode 22 side after the electrolysis contains oxygen generated on the surface of the anode 22 by the electrolysis, and this oxygen can be prevented from coming into contact with the anode 22 again. In addition, since the anode 22 and the cathode 23 are separated by the diaphragm 24, it is possible to prevent this oxygen from coming into contact with the cathode 23. Therefore, it is possible to suppress deterioration of the electrode due to contact with oxygen. Therefore, organic substances can be generated more efficiently even in a low temperature environment.

  Further, the plurality of anodes 22 and the plurality of cathodes 23 are formed in a flat plate shape and are arranged in parallel, and the anodes 22 and 23 adjacent to each other among the plurality of anodes 22 and the plurality of cathodes 23 are assembled. The space distance between the electrodes of the anode 22 and the cathode 23 forming this set is 2.5 mm or less. As a result, in the electrolysis, the narrower the gap between the electrodes, the better the efficiency. On the other hand, the aqueous solution is less likely to flow between the electrodes, and the removal of bubbles on the electrode surface is hindered to maintain good efficiency. However, by setting the intervals between the plurality of anodes 22 and the plurality of cathodes 23 within the above range, the efficiency of electrolysis and its maintenance can be appropriately balanced.

  A plurality of openings are provided in at least one of the plurality of anodes 22 and the plurality of cathodes 23. Since it did in this way, aqueous solution can flow more easily between electrodes, the bubble removal of the electrode surface is accelerated | stimulated, and the efficiency of electrolysis can be maintained more appropriately.

  Moreover, the control part 50 controls the pH of the aqueous solution at the time of electrolysis within the range of 5-10 by adding a chemical | medical agent (base) to aqueous solution, for example, the quantity (namely, carbon dioxide is included). The pH of the aqueous solution can be easily and accurately controlled by adjusting the addition amount of the base, compared with the case where the pH is controlled by the concentration. Therefore, organic substances can be generated more efficiently even in a low temperature environment.

  In addition, an organic matter extraction unit 30 that extracts an organic matter is provided, and the organic matter extraction unit 30 extracts an organic matter contained in a gas generated by electrolysis by the electrolytic synthesis unit 20 and electrolysis by the electrolytic synthesis unit 20. It has a liquid organic substance extraction unit 32 that extracts organic substances contained in the aqueous solution after being removed. Since it did in this way, the gaseous organic substance and water-soluble organic substance which were produced by electrolysis can be obtained.

  The liquid organic substance extraction unit 32 further includes a treated aqueous solution recovery unit 40 that sends the aqueous solution after the organic substance is extracted to the gas absorption unit 10. Since it did in this way, carbon dioxide can be included again in the aqueous solution after electrolysis, and it can reuse.

  Although the present invention has been described with reference to the preferred embodiments, the organic substance generation device and the organic substance generation method of the present invention are not limited to the configurations of the above-described embodiments.

  For example, in the above-described embodiment, the gas absorption unit 10 is configured to supply gaseous carbon dioxide to the gas phase part of the gas absorption tank 11, but is not limited thereto. For example, like the gas absorption part 10A of the organic substance generation apparatus 1A shown in FIG. 5, the microbubble generator 19 is provided in the pH measurement pipe 12A connected to the liquid phase part of the gas absorption tank 11 at one end and the other end. It is good also as the structure comprised. In this gas absorption part 10A, carbon dioxide is supplied to the gas phase part of the gas absorption tank 11, and the treated aqueous solution is sprayed to the gas phase part from the sprayer 11a, thereby absorbing the carbon dioxide in the mist-like aqueous solution. Further, carbon dioxide is also supplied to the microbubble generator 19, and carbon dioxide is absorbed into the aqueous solution by generating microbubbles of carbon dioxide in the aqueous solution flowing in the pH measuring pipe 12A by the pH measuring pump 13. Let Water from the outside is supplied to the liquid phase part of the gas absorption tank 11. By comprising in this way, carbon dioxide can be absorbed more by aqueous solution. In FIG. 5, the same components as those in the above-described embodiment are denoted by the same reference numerals and description thereof is omitted.

  Moreover, in embodiment mentioned above, it was the structure which flows the aqueous solution produced | generated by the gas absorption part 10 in one direction so that the inside of the some accommodating part 25 of the electrolysis tank 21 may be passed in the electrolytic synthesis part 20. FIG. However, the present invention is not limited to this. For example, like the electrolytic synthesis unit 20A of the organic matter generating apparatus 1B shown in FIG. 6, the other end branched into a plurality of transfer pipes 17 is connected only to the housing part 25 (cathode housing part 25) housing a plurality of cathodes 23. Then, the aqueous solution generated by the gas absorption unit 10 is allowed to flow only in the cathode housing portion 25. The circulation pipe 201 having one end connected to the aqueous solution discharge portion of the anode-side extraction tank 31a and the other branched end connected to the housing portion 25 (anode housing portion 25) housing the plurality of anodes 22; A circulation pump 202 for flowing an electrolyte aqueous solution different from the aqueous solution from one end to the other end of the circulation pipe 201 and a tank 203 for storing the electrolyte aqueous solution are provided, and the electrolyte aqueous solution is extracted from the tank 203, the anode accommodating portion 25 and the anode side. An independent circulation system that circulates in the tank 31a is configured. In FIG. 6, the same components as those in the above-described embodiment are denoted by the same reference numerals and description thereof is omitted.

Examples of the aqueous electrolyte solution include lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na ₂ CO ₃ ), potassium carbonate (K ₂ CO ₃ ), lithium carbonate ( One or more substances selected from LiHCO ₃ ), sodium bicarbonate (NaHCO ₃ ), potassium bicarbonate (KHCO ₃ ), potassium sulfate (K ₂ SO ₄ ) and sulfuric acid (H ₂ SO ₄ ) were dissolved. Is. Of course, these are examples, and other substances may be used as long as they do not contradict the purpose of the present invention as long as they are substances that become the solute of the aqueous electrolyte solution.

  By doing in this way, the aqueous solution containing carbon dioxide flows in one direction only in the cathode housing portion 25 in which the plurality of cathodes 23 of the plurality of housing portions 25 are housed, and the cathode housing portion 25. Immediately after passing through the electrolysis tank 21 is discharged. Further, another electrolyte aqueous solution isolated from the aqueous solution flows in one direction only in the anode housing portion 25 in which the plurality of anodes 22 among the plurality of housing portions 25 are housed, and passes through the anode housing portion 25. Immediately after being discharged from the electrolysis tank 21.

  Therefore, the aqueous solution on the anode 22 side after the electrolysis contains oxygen generated on the surface of the anode 22 by the electrolysis, and this oxygen can be prevented from coming into contact with the anode 22 again. Since the cathode 23 is separated from the cathode 23, it is possible to prevent the oxygen from coming into contact with the cathode 23. Further, in a configuration in which the aqueous solution after electrolysis is reused, oxygen generated by electrolysis may be dissolved in such a reused aqueous solution. By isolating the aqueous solution, it is possible to prevent dissolved oxygen from coming into contact with the cathode 23. Thereby, deterioration of the electrode due to contact with oxygen can be suppressed. Therefore, organic substances can be generated more efficiently even in a low temperature environment.

  In addition, embodiment mentioned above only showed the typical form of this invention, and this invention is not limited to embodiment. That is, those skilled in the art can implement various modifications in accordance with conventionally known knowledge without departing from the scope of the present invention. Of course, such modifications are also included in the scope of the present invention as long as the organic substance generating apparatus and the organic substance generating method of the present invention are configured.

  Hereinafter, the present invention will be described more specifically with reference to examples.

Example 1
In the organic substance generation apparatus 1 of the above-described embodiment, (1) the pH of the aqueous solution generated in the gas absorption unit 10 is controlled to be a plurality of different pH values included in the range of 4 to 11, The total amount of organic carbon (TOC; total organic carbon) contained in the aqueous solution after electrolysis and gas generated during the organic substance generation treatment for 1 hour was measured. (2) Potassium sulfate (K ₂ SO ₄ ) and sulfuric acid (H ₂ SO ₄ ), sodium bicarbonate (NaHCO ₃ ), or sodium carbonate (Na ₂ CO ₃ ) (3) A voltage of 3V is applied between the plurality of anodes 22 and the plurality of cathodes 23, and (4) the inter-electrode spatial distance of each of the plurality of anodes 22 and the plurality of cathodes 23 is set to 0.5 mm. 5) The aperture ratio of the plurality of anodes 22 and the plurality of cathodes 23 is set to 30%, (6) the flow rate of the aqueous solution flowing in the plurality of accommodating portions 25 is set to 2.0 m / min, and (7) the temperature of the aqueous solution is set to 30. C. FIG. 7 shows a graph obtained by plotting the TOC ratio at each pH value, assuming that the TOC when the pH is 5.0 is 1.0.

  As shown in FIG. 7, when the pH of the aqueous solution is included in the range of 5 to 10, the TOC ratio is 1.0 or more, and when it is included in the range of 5.5 to 9.6, the TOC ratio is 1. The TOC ratio is 1.5 or more when it is 25 or more and included in the range of 6.2 to 8.8. From this, when the pH of the aqueous solution produced | generated in the gas absorption part 10 (namely, pH of the aqueous solution in the case of electrolysis) is contained in the said range, an organic substance can be produced | generated efficiently.

(Example 2)
In the organic matter generating apparatus 1 of the above-described embodiment, (1) the inter-electrode spatial distances of the plurality of anodes 22 and the plurality of cathodes 23 are set to a plurality of different values, and the organic matter generating process is performed for one hour for each set value. The total amount of organic carbon (TOC) contained in the gas generated during the operation and in the aqueous solution after electrolysis was measured. In the production of the organic matter, (2) the pH of the aqueous solution is controlled to 8.5, (3) sodium bicarbonate (NaHCO ₃ ) is used as the agent used for pH control, and (4) the plurality of anodes 22 and the plurality of cathodes. A voltage of 3 V is applied between the plurality of anodes 23, (5) the aperture ratio of the plurality of anodes 22 and the plurality of cathodes 23 is set to 30%, and (6) the flow rate of the aqueous solution flowing in the plurality of accommodating portions 25 is 6.0 m / (7) The temperature of the aqueous solution was 30 ° C. FIG. 8 shows a graph obtained by plotting the TOC ratio at each inter-electrode spatial distance setting value, assuming that the TOC when the inter-electrode spatial distance is 0 mm is 1.0.

  As shown in FIG. 8, when the inter-electrode spatial distance is included in the range of 0 mm to 2.5 mm, the TOC ratio is 1.0 or more, and the inter-electrode spatial distance is included in the range of 0.5 mm to 2.0 mm. TOC ratio is 1.5 or more. From this, organic substances can be efficiently generated when the inter-electrode spatial distances of the plurality of anodes 22 and the plurality of cathodes 23 are within the above range.

(Example 3)
In the organic matter generation device 1 of the above-described embodiment, (1) the aperture ratios of the plurality of electrodes 22 and the plurality of cathodes 23 are set to a plurality of different values, and the organic matter generation processing is performed for one hour for each set value. The total organic carbon content (TOC) contained in the generated gas and the aqueous solution after electrolysis was measured. In the production of the organic matter, (2) the pH of the aqueous solution is controlled to 8.5, (3) potassium bicarbonate (KHCO ₃ ) is used as the agent used for pH control, and (4) the plurality of anodes 22 and the plurality of cathodes. A voltage of 3 V is applied between the electrodes 23, (5) the inter-electrode spatial distance of each of the plurality of anodes 22 and the plurality of cathodes 23 is 0.5 mm, and (6) the flow velocity of the aqueous solution flowing in the plurality of housing portions 25 Was 2.0 m / min, and (7) the temperature of the aqueous solution was 30 ° C. Then, FIG. 9 shows a graph obtained by plotting the TOC ratio at each aperture ratio setting value, assuming that the TOC when the aperture ratio is 0% is 1.0.

  As shown in FIG. 9, the TOC ratio is 1.2 or more when the aperture ratio is included in the range of 10% to 70%, and the TOC ratio is 1.4 when included in the range of 20% to 60%. That's it. From this, when the aperture ratios of the plurality of anodes 22 and the plurality of cathodes 23 are within the above range, organic substances can be efficiently generated.

Example 4
In the organic matter generating apparatus 1 of the above-described embodiment, (1) the flow rate of the aqueous solution flowing in the plurality of accommodating portions 25 is set to a plurality of different values, and the organic matter generating process is performed for one hour for each set value. The total organic carbon content (TOC) contained in the generated gas and the aqueous solution after electrolysis was measured. In the production of the organic matter, (2) the pH of the aqueous solution is controlled to 8.5, (3) sodium bicarbonate (NaHCO ₃ ) is used as the agent used for pH control, and (4) the plurality of anodes 22 and the plurality of cathodes. A voltage of 3 V is applied between the electrodes 23, (5) the inter-electrode spatial distance of the plurality of anodes 22 and the plurality of cathodes 23 is 0.5 mm, and (6) the aperture ratio of the plurality of anodes 22 and the plurality of cathodes 23. Was 30%, and (7) the temperature of the aqueous solution was 30 ° C. FIG. 9 shows a graph obtained by plotting the TOC ratio at each flow rate setting value, assuming that the TOC when the flow rate is 0 m / min is 1.0.

  As shown in FIG. 10, when the flow velocity is included in the range of 0 m / min to 11 m / min, the TOC ratio is 1.00 or more, and when it is included in the range of 2 m / min to 10 m / min, the TOC ratio is 1.10 or more When the TOC ratio is within the range of 4 m / min to 9 m / min, the TOC ratio is 1.15 or more. When the TOC ratio is within the range of 6 m / min to 8 m / min, the TOC ratio is 1.0 or more. It becomes. On the other hand, when the flow rate exceeds 11 m / min, the TOC ratio is less than 1.00, and the efficiency of organic matter generation is deteriorated. For this reason, organic substances can be efficiently generated when the flow rate of the aqueous solution flowing in the plurality of accommodating portions 25 falls within the above range.

(Consideration of results)
From the above results, by controlling or setting the pH of the aqueous solution, the inter-electrode spatial distance, the electrode opening ratio, and the aqueous solution flow rate within specific ranges, organic substances can be efficiently generated while keeping the aqueous solution at a low temperature. I was able to.

1 Organic matter generation device 10 Gas absorption part (aqueous solution generation part)
11 Gas absorption tank (container for generation)
12 Pipe for pH measurement 13 Pump for pH measurement 14 pH meter 15 Chemical tank for pH adjustment 16 Drug injection pump 17 Transfer pipe (moving means)
18 Transfer pump (moving means, flow means)
20 Electrolytic synthesis part (electrolysis part)
21 Electrolysis tank (electrolysis vessel)
22 Anode 23 Cathode 24 Diaphragm 25 Storage part 30 Organic substance extraction part 31 Gaseous organic substance extraction part (Gaseous organic substance extraction means)
32 Liquid organic matter extraction unit (liquid organic matter extraction means)
40 Treated aqueous solution recovery unit (liquid feeding means)
50 Control unit (pH control unit)

Claims (12)

A method of producing an organic substance by electrolyzing an aqueous solution containing carbon dioxide,
Controlling the pH of the aqueous solution during the electrolysis within a range of 5 to 10,
An aqueous solution generating step of absorbing the carbon dioxide into water in the generating container to generate the aqueous solution;
A moving step of moving the aqueous solution from the production vessel to a separate electrolysis vessel;
Electrolyzing the aqueous solution in the electrolysis vessel, and
Controlling the pH of the aqueous solution within the range of 5 to 10 in the production container;
In the electrolysis step, the aqueous solution in the electrolysis vessel is caused to flow at a flow rate of 4 m / min to 9 m / min,
Carbon dioxide gas is not moved to the electrolysis vessel. A method for producing an organic substance by electrolyzing an aqueous solution containing carbon dioxide at an anode and a cathode,
Controlling the pH of the aqueous solution during the electrolysis within a range of 5 to 10,
An organic substance generation method comprising an aqueous solution generation step of generating water by absorbing carbon dioxide into water.   The method for producing an organic substance according to claim 1 or 2, wherein the pH of the aqueous solution during the electrolysis is controlled within a range of 5 to 10 by adding a base to the aqueous solution. An aqueous solution generator for generating an aqueous solution containing carbon dioxide;
An electrolysis unit for electrolyzing the aqueous solution generated by the aqueous solution generation unit;
A pH control unit for controlling the pH of the aqueous solution during the electrolysis within a range of 5 to 10,
The aqueous solution generator has a generation container in which the aqueous solution is generated by absorbing carbon dioxide in water;
The electrolysis unit has an electrolysis container separate from the production container in which the aqueous solution is electrolyzed,
The pH controller controls the pH of the aqueous solution within the range of 5 to 10 in the production container;
Moving means for moving the aqueous solution from the production vessel to the electrolysis vessel;
A flow means for flowing the aqueous solution in the electrolysis vessel at a flow rate of 4 m / min to 9 m / min;
An organic matter generating system characterized in that carbon dioxide gas is not moved to the electrolysis vessel. An aqueous solution generator for generating an aqueous solution containing carbon dioxide;
An electrolysis unit for electrolyzing the aqueous solution generated by the aqueous solution generation unit with an anode and a cathode;
A pH controller for controlling the pH of the aqueous solution in the range of 5 to 10 during the electrolysis.   The electrolysis section includes a plurality of anodes and a plurality of cathodes alternately arranged in the electrolysis container, and a plurality of the plurality of anodes and the plurality of cathodes individually accommodated in the electrolysis container. The aqueous solution is divided into the plurality of accommodating portions, flows in one direction, and is discharged from the electrolysis container immediately after passing through. The organic matter generation system according to claim 4 or 5, wherein   The electrolysis section includes a plurality of anodes and a plurality of cathodes alternately arranged in the electrolysis container, and a plurality of the plurality of anodes and the plurality of cathodes individually accommodated in the electrolysis container. And the aqueous solution flows in one direction only within the housing portion in which the plurality of cathodes are housed among the plurality of housing portions. Immediately after passing, another electrolyte aqueous solution discharged from the electrolysis vessel and isolated from the aqueous solution flows in one direction only within the housing portion in which the plurality of anodes are housed among the plurality of housing portions. The organic matter generating system according to claim 4, wherein the organic matter generating system is configured to be discharged from the electrolysis container immediately after passing through the housing portion. The plurality of anodes and the plurality of cathodes are formed in a flat plate shape and are arranged in parallel,
Of the plurality of anodes and the plurality of cathodes, adjacent anodes and cathodes each form a set,
The organic matter generation system according to claim 6 or 7, wherein a space distance between the anode and the cathode forming the set is 2.5 mm or less.   9. The organic substance generating system according to claim 8, wherein at least one of the plurality of anodes and the plurality of cathodes is provided with one or a plurality of openings.   The said pH control part controls the pH of the said aqueous solution in the case of the said electrolysis in the range of 5-10 by adding a base to the said aqueous solution, The any one of Claims 4-9 characterized by the above-mentioned. The organic matter generation system described in 1. It further comprises an organic matter extraction part for extracting organic matter,
The organic matter extraction unit extracts the organic matter contained in the aqueous solution after the electrolysis by the electrolysis unit and the gaseous organic matter extraction means for extracting the organic matter contained in the gas generated by the electrolysis by the electrolysis unit It has at least one of liquid organic substance extraction means, The organic substance production | generation system as described in any one of Claims 4-10 characterized by the above-mentioned. The organic matter extraction unit has the liquid organic matter extraction means,
12. The organic matter generating system according to claim 11, further comprising a liquid sending means for sending the aqueous solution after the organic matter is extracted by the liquid organic matter extracting means to the aqueous solution producing section.

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