CN116497372A - Electrolysis system and method for carbon dioxide - Google Patents

Electrolysis system and method for carbon dioxide Download PDF

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Publication number
CN116497372A
CN116497372A CN202210166509.8A CN202210166509A CN116497372A CN 116497372 A CN116497372 A CN 116497372A CN 202210166509 A CN202210166509 A CN 202210166509A CN 116497372 A CN116497372 A CN 116497372A
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cathode
mixture
anode
carbon dioxide
reactant
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廖德超
庄荣仁
李奕成
陈浩铭
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Nan Ya Plastics Corp
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Nan Ya Plastics Corp
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/23Carbon monoxide or syngas
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/24Halogens or compounds thereof
    • C25B1/26Chlorine; Compounds thereof
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/50Processes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/08Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/083Separating products
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/08Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/087Recycling of electrolyte to electrochemical cell
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70Assemblies comprising two or more cells

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Abstract

The invention discloses an electrolysis system and method of carbon dioxide. The electrolysis system for carbon dioxide includes an electrochemical electrolysis device and an absorption unit in fluid communication with the electrochemical electrolysis device. The electrochemical electrolysis device electrolyzes a cathode reactant and an anode reactant to form a cathode mixture and an anode mixture, respectively. Wherein the cathode reactant comprises carbon dioxide or a compound comprising bicarbonate or carbonate, the cathode mixture comprises carbon monoxide and hydrogen, and the anode mixture comprises chlorine. The absorption unit processes the cathode mixture and separates a synthesis gas comprising carbon monoxide and hydrogen. The electrolysis system and method of carbon dioxide can slow down the greenhouse effect and make the reduction product component of carbon dioxide simple and reusable.

Description

Electrolysis system and method for carbon dioxide
Technical Field
The present invention relates to a system and a method for electrolyzing carbon dioxide, and more particularly, to a system and a method for electrolyzing carbon dioxide capable of generating synthesis gas and chlorine.
Background
Carbon dioxide gas generated by burning petrochemical materials is a main cause of greenhouse effect. In order to alleviate the global warming problem, how to convert carbon dioxide gas into other reusable energy sources is one of the important research and development targets at present.
In the prior art, various techniques for reducing carbon dioxide are disclosed. One such technique is to combine a photocatalyst with a water splitting system to reduce carbon dioxide in a manner similar to that of a plant photosynthesis system. The water is decomposed by photocatalysis to generate hydrogen ions, and then the hydrogen ions are used for reducing carbon dioxide. However, this apparatus is a batch reaction apparatus, which is disadvantageous for handling a large amount of carbon dioxide.
Another technique for reducing carbon dioxide is to dissolve carbon dioxide in an electrolyte and reduce carbon dioxide by means of electrocatalysis (electrolysis). However, the diffusion capacity and concentration of carbon dioxide are affected by time, which in turn affects the conversion of carbon dioxide. In addition, the reduction products of carbon dioxide include various hydrocarbons, such as methane, methanol, ethane, ethanol, acetic acid, or ethylene, and not all products can be used as fuel or as a base material for other chemicals, so that a plurality of separation and purification steps are required, and the steps are complex.
Therefore, how to reduce carbon dioxide to alleviate the problem of greenhouse effect and make the reduction product component of carbon dioxide simple and reusable has become one of the important problems to be solved by this industry.
Disclosure of Invention
The invention aims to solve the technical problem of providing a carbon dioxide electrolysis system and a carbon dioxide electrolysis method aiming at the defects in the prior art.
In order to solve the technical problems, one technical scheme adopted by the invention is to provide an electrolysis system of carbon dioxide. The electrolysis system for carbon dioxide includes an electrochemical electrolysis device and an absorption unit in fluid communication with the electrochemical electrolysis device. The electrochemical electrolysis device electrolyzes a cathode reactant and an anode reactant to form a cathode mixture and an anode mixture, respectively. Wherein the cathode reactant comprises carbon dioxide or a compound comprising bicarbonate or carbonate, the cathode mixture comprises carbon monoxide and hydrogen, and the anode mixture comprises chlorine. The absorption unit processes the cathode mixture and separates a synthesis gas comprising carbon monoxide and hydrogen.
Preferably, the absorption unit divides the cathode mixture into a cathode gas product comprising the synthesis gas and a reflux comprising bicarbonate, carbonate or hydroxide, which reflux is refluxed to the electrochemical electrolysis device.
Preferably, the electrolysis system of carbon dioxide further comprises: a first reactant preparation unit in fluid communication between the electrochemical electrolysis device and the absorption unit, the first reactant preparation unit receiving the reflux and providing the cathode reactant to the electrochemical electrolysis device.
Preferably, the cathode mixture comprises a cathode gas mixture and a cathode liquid mixture, and the absorption unit processes the cathode gas mixture.
Preferably, the catholyte mixture comprises a catholyte mixture comprising metal ions, hydroxide ions or metal hydroxides.
Preferably, the electrolysis system of carbon dioxide further comprises: and the first gas-liquid separation unit is in fluid connection and fluid communication between the electrochemical electrolysis equipment and the absorption unit, and divides the cathode mixture into a cathode gas mixture and a cathode liquid mixture.
Preferably, the electrolysis system of carbon dioxide further comprises: and a first liquid treatment unit in fluid communication with the electrochemical electrolysis device, the first liquid treatment unit treating the catholyte mixture to produce a first treatment liquid, the first treatment liquid being returned to the electrochemical electrolysis device.
Preferably, the electrolysis system of carbon dioxide further comprises: a first reactant preparation unit in fluid communication between the electrochemical electrolysis device and the first liquid treatment unit, the first reactant preparation unit receiving the first treatment liquid and providing a cathode reactant to the electrochemical electrolysis device.
Preferably, the anode mixture comprises an anode gas mixture and an anode liquid mixture.
Preferably, the electrolysis system of carbon dioxide further comprises: and the second gas-liquid separation unit is in fluid connection and fluid communication with the electrochemical electrolysis equipment, and divides the anode mixture into an anode gas mixture and an anode liquid mixture.
Preferably, the electrolysis system of carbon dioxide further comprises: and a second liquid treatment unit in fluid communication with the electrochemical electrolysis device, the second liquid treatment unit treating the anode liquid mixture to produce a second treatment liquid, the second treatment liquid being returned to the electrochemical electrolysis device.
Preferably, the electrolysis system of carbon dioxide further comprises: and a second reactant preparation unit in fluid communication between the electrochemical electrolysis device and the second liquid treatment unit, the second reactant preparation unit receiving the second treatment liquid and providing the anode reactant to the electrochemical electrolysis device.
Preferably, the electrochemical electrolysis device comprises a plurality of electrolysis cells; each electrolysis unit comprises a cathode electrode positioned in a cathode cavity, an anode electrode positioned in an anode cavity and an ion exchange membrane clamped between the cathode electrode and the anode electrode.
Preferably, the cathode electrode is arranged in the cathode chamber, a cathode catalyst is formed on the cathode electrode, the anode electrode is arranged in the anode chamber, an anode catalyst is formed on the anode electrode, and every two adjacent electrolysis units are separated by an insulating plate; wherein the material of the cathode catalyst comprises iron, cobalt, nickel, copper, ruthenium, rhodium, silver, iridium, platinum, gold, titanium or a carbon compound containing any one of the metals, and the material of the anode catalyst comprises ruthenium, rhodium, iridium, titanium or a metal halide, a metal oxide or a metal hydroxide containing any one of the metals.
Preferably, the cathode chamber has an inlet for receiving the cathode reactant and an outlet for discharging the cathode mixture, and the anode chamber has an inlet for receiving the anode reactant and an outlet for discharging the anode mixture.
Preferably, the cathode chamber has an inlet for receiving the cathode reactant and two outlets for discharging the cathode mixture, and the anode chamber has an inlet for receiving the anode reactant and two outlets for discharging the anode mixture.
Preferably, the cathode reactant further comprises a catholyte comprising bicarbonate or carbonate; the anode reactant also comprises an anode electrolyte, and the anode electrolyte contains chloride ions.
Preferably, the anolyte comprises salts containing chloride ions.
In order to solve the above technical problems, another technical solution adopted in the present invention is to provide an electrolysis method of carbon dioxide. The method for electrolyzing carbon dioxide comprises the following steps: electrolyzing a cathode reactant and an anode reactant by using an electrochemical electrolysis device to form a cathode mixture and an anode mixture respectively; and treating the cathode mixture with an absorption unit to separate a synthesis gas comprising carbon monoxide and hydrogen. Wherein the cathode reactant comprises carbon dioxide or a carbonate or bicarbonate containing compound, the cathode mixture comprises carbon monoxide and hydrogen, and the anode mixture comprises chlorine.
Preferably, after the absorption unit processes the cathode mixture, the cathode mixture is separated into a cathode gas product and a reflux, wherein the cathode gas product comprises synthesis gas, and the reflux comprises bicarbonate, carbonate or hydroxide; wherein the method for electrolyzing carbon dioxide further comprises: and refluxing the reflux liquid to the electrochemical electrolysis equipment.
Preferably, the electrolysis method of carbon dioxide further comprises: the reflux is delivered to a first reactant preparation unit that provides the cathode reactant to the electrochemical electrolysis device.
Preferably, the cathode mixture comprises a cathode gas mixture and a cathode liquid mixture, the cathode liquid mixture comprising metal ions, hydroxide ions or metal hydroxides.
One of the advantages of the present invention is that the electrolysis system and method for carbon dioxide provided by the present invention can decompose greenhouse gases (carbon dioxide) by the technical scheme that the cathode reactant includes carbon dioxide or carbonate or bicarbonate-containing compounds, the cathode mixture includes carbon monoxide and hydrogen, the anode mixture includes chlorine, and the absorption unit processes the cathode mixture and separates a synthesis gas including carbon monoxide and hydrogen, thereby producing synthesis gas (carbon monoxide and hydrogen) that can be used as fuel.
For a further understanding of the nature and the technical aspects of the present invention, reference should be made to the following detailed description of the invention and the accompanying drawings, which are provided for purposes of reference only and are not intended to limit the invention.
Drawings
FIG. 1 is a functional block diagram of a carbon dioxide electrolysis system according to a first embodiment of the invention.
FIG. 2 is a schematic perspective view of an electrochemical electrolysis apparatus according to the present invention.
FIG. 3 is a schematic side sectional view of an electrochemical electrolysis apparatus according to a first embodiment of the present invention.
FIG. 4 is a functional block diagram of a carbon dioxide electrolysis system according to a second embodiment of the invention.
FIG. 5 is a functional block diagram of a carbon dioxide electrolysis system according to a third embodiment of the invention.
FIG. 6 is a schematic side sectional view of an electrochemical electrolysis apparatus according to a third embodiment of the present invention.
FIG. 7 is a functional block diagram of a carbon dioxide electrolysis system according to a fourth embodiment of the invention.
FIG. 8 is a flow chart of the method of electrolyzing carbon dioxide of the present invention.
Detailed Description
The following is a specific example to illustrate embodiments of the disclosed "electrolysis system and method for carbon dioxide" and those skilled in the art will appreciate the advantages and effects of the present invention from the disclosure herein. The invention is capable of other and different embodiments and its several details are capable of modification and variation in various respects, all from the point of view and application, all without departing from the spirit of the present invention. The drawings of the present invention are merely schematic illustrations, and are not intended to be drawn to actual dimensions. The following embodiments will further illustrate the related art content of the present invention in detail, but the disclosure is not intended to limit the scope of the present invention. In addition, the term "or" as used herein shall include any one or combination of more of the associated listed items as the case may be.
The invention provides an electrolysis system for carbon dioxide, which comprises an electrochemical electrolysis device and an absorption unit which are in fluid communication. Electrochemical electrolysis equipment is used for reducing carbon dioxide to achieve the effect of reducing the greenhouse effect problem, and can simultaneously produce alkaline liquid products with commercial application. The absorption unit is used for separating carbon dioxide and products after carbon dioxide reduction to obtain high-content synthesis gas (mixed gas of carbon monoxide and hydrogen), and can be directly used as fuel or used as a basic raw material of other chemicals. The gas phase product produced by the cathode may comprise methane, ethane, ethylene or mixtures thereof in addition to the synthesis gas, but still has the synthesis gas as the main component.
The electrochemical electrolysis device of the invention can electrolyze a cathode reactant and an anode reactant and respectively form a cathode mixtureThe compound is mixed with an anode. Specifically, the cathode reactant includes carbon dioxide gas and a catholyte, and the anode reactant includes an anolyte. The half-reactions of the cathode reactants that occur at the cathode are: CO 2(g) +H 2 O (l) +2e - →CO (g) +2OH - (aq) 、2H 2 O (l) +2e - →H 2(g) +2OH - (aq) Na (sodium carbonate) + (aq) +OH - (aq) →NaOH (l) The method comprises the steps of carrying out a first treatment on the surface of the The half-reactions of the anode reactants that occur at the anode are: 2Cl - →Cl 2(g) +2e - . After electrolysis, the cathode mixture contains carbon monoxide and hydrogen generated by the electrolysis reaction, liquid sodium hydroxide and catholyte. The anode mixture includes electrolytically generated chlorine gas and an anolyte.
The carbon dioxide gas is introduced into the cathode, so that the problems of low carbon dioxide conversion rate and unstable electrolytic reaction caused by slow diffusion speed of carbon dioxide in aqueous solution are avoided. And, the cathode mixture produced by the electrolysis reaction includes a high content of synthesis gas, which can be directly used as fuel. And by using the absorption unit, the non-electrolyzed carbon dioxide in the cathode mixture can be absorbed, so that the high-purity synthesis gas is further obtained.
From this, it is clear that the electrolysis system of carbon dioxide according to the present invention can convert carbon dioxide into carbon monoxide and hydrogen at the cathode, and not only decompose greenhouse gases (carbon dioxide), but also produce synthesis gases (carbon monoxide and hydrogen) that can be used as fuel. Because of the high concentration of the synthesis gas, the synthesis gas can be directly used as a base raw material of fuel or other chemicals without complex separation or purification steps. In other embodiments, the cathode reactant may also be a bicarbonate or carbonate containing compound.
The catholyte may be an aqueous solution of an electrolyte containing sodium hydroxide, sodium bromide, sodium bicarbonate, sodium sulfate, sodium phosphate, sodium hydrogen phosphate, lithium hydroxide, lithium bromide, lithium bicarbonate, lithium sulfate, lithium phosphate, lithium hydrogen phosphate, potassium hydroxide, potassium bromide, potassium hydrogen carbonate, potassium sulfate, potassium phosphate, potassium hydrogen phosphate, or any combination thereof. In a preferred embodiment, the catholyte comprises bicarbonate or carbonate, preferably the catholyte is an aqueous solution comprising sodium bicarbonate, for example: carbon dioxide may be dissolved in aqueous sodium hydroxide to form an aqueous sodium bicarbonate solution. The concentration of the electrolyte in the catholyte is at least 0.001M, and the concentration of the electrolyte can reach the saturation concentration.
The anolyte may be an aqueous solution of an electrolyte containing sodium hydroxide, sodium bromide, sodium bicarbonate, sodium sulfate, sodium phosphate, sodium hydrogen phosphate, lithium hydroxide, lithium bromide, lithium bicarbonate, lithium sulfate, lithium phosphate, lithium hydrogen phosphate, potassium hydroxide, potassium bromide, potassium hydrogen carbonate, potassium sulfate, potassium phosphate, potassium hydrogen phosphate, or any combination thereof. In a preferred embodiment, the anolyte comprises chloride ions (particularly chloride ion-containing salts), and preferably the anolyte is an aqueous solution comprising sodium chloride. The concentration of the electrolyte in the anolyte is at least 0.001M, and the concentration of the electrolyte can reach the saturation concentration.
First embodiment
Referring to fig. 1, a first embodiment of the present invention provides an electrolysis system for carbon dioxide, which includes: electrochemical electrolysis apparatus 1, a first reactant preparation unit 2, a second reactant preparation unit 3, a first gas-liquid separation unit 4, a second gas-liquid separation unit 5, and absorption unit 6.
The electrochemical electrolysis device 1 is in fluid communication with the first reactant formulation unit 2 to receive the cathode reactant A1 provided by the first reactant formulation unit 2. The electrochemical electrolysis device 1 is in fluid communication with the second reactant formulation unit 3 to receive the anode reactant A2 provided by the second reactant formulation unit 3. The electrochemical electrolysis apparatus 1 electrolyzes the cathode reactant A1 and the anode reactant A2, and forms a cathode mixture B1 and an anode mixture B2, respectively. Wherein the cathode reactant A1 is prepared by the first reactant preparation unit 2 after receiving the catholyte E1 and carbon dioxide gas, and the anode reactant A2 is prepared by the second reactant preparation unit 3 after receiving the anolyte E2.
The electrochemical electrolysis device 1 is in fluid communication with a first gas-liquid separation unit 4 to separate the gas phase component from the liquid phase component in the cathode mixture B1. The cathode mixture B1 can be divided into a cathode gas mixture V1 and a cathode liquid mixture L1 by the first gas-liquid separation unit 4. Specifically, the cathode gas mixture V1 includes carbon dioxide, carbon monoxide and hydrogen. The catholyte mixture L1 contains liquid sodium hydroxide and the catholyte E1, that is, the catholyte mixture L1 contains metal ions, hydroxide ions or metal hydroxides. From this, it is understood that the electrolysis system of carbon dioxide of the present invention can produce both the cathode gas mixture V1 and the cathode liquid mixture L1 having economic values.
The electrochemical electrolysis device 1 is in fluid communication with a second gas-liquid separation unit 5 to separate the gas phase component from the liquid phase component in the anode mixture B2. The anode mixture B2 can be divided into an anode gas mixture V2 and an anode liquid mixture L2 by the second gas-liquid separation unit 5. Specifically, the anode gas mixture V2 includes chlorine gas, and the anolyte mixture L2 includes the anolyte E2.
The absorption unit 6 is in fluid communication with the first gas-liquid separation unit 4 for treating the cathode gas mixture V1, and the absorption unit 6 absorbs carbon dioxide in the cathode gas mixture V1 to separate carbon monoxide from hydrogen. Specifically, the catholyte E1 is passed to the absorption unit 6, and the catholyte E1 is brought into contact with the cathode gas mixture V1, at which time carbon dioxide is dissolved in the catholyte E1 from the cathode gas mixture V1.
Thus, after the cathode gas mixture V1 contacts the catholyte E1, a cathode gas product P1 and a reflux R1 are formed. The cathode gas product P1 comprises carbon monoxide and hydrogen. The reflux liquid R1 contains a catholyte E1, liquid sodium hydroxide (or liquid alkali) and carbon dioxide. It is noted that liquid sodium hydroxide reacts with carbon dioxide to form aqueous sodium bicarbonate solution, which can be used as catholyte E1. Thus, the reflux liquid R1 can be refluxed to the electrochemical electrolysis apparatus 1 and reused as the cathode reactant A1. In a preferred embodiment, the reflux liquid R1 is first delivered to the first reactant preparation unit 2, and then delivered to the electrochemical electrolysis apparatus 1 after being appropriately prepared. Specifically, the reflux liquid R1 contains bicarbonate, carbonate or hydroxide.
The electrochemical electrolysis device 1 and the absorption unit 6 can form a circulation pipeline, so that the electrolysis system of the carbon dioxide can stably generate the cathode gas product P1 and the cathode liquid mixture L1 with economic value, and the use efficiency of the cathode reactant A1 can be improved.
Referring to fig. 2 and 3, the chemical electrolysis apparatus 1 of the present invention includes a plurality of electrolysis units 10. In the first embodiment, a plurality of electrolytic cells 10 are arranged in series with an insulating plate 13 interposed between each two adjacent electrolytic cells 10. In some embodiments, the number of electrolysis cells 10 is 3 to 30.
In addition, although the electrolytic cells 10 are illustrated as being arranged in series in fig. 2, the present invention is not limited to this in practical application, and a plurality of electrolytic cells 10 may be arranged in parallel. For example, several electrolysis units 10 may be arranged in series to form an electrolysis module, and then several electrolysis modules are connected in parallel to form an electrolysis assembly to increase the carbon dioxide gas throughput and/or increase the concentration of the cathode gas product P1.
Referring to fig. 2 and 3, each of the electrolytic cells 10 includes a cathode electrode 14 disposed in a cathode chamber 11, an anode electrode 15 disposed in an anode chamber 12, and an ion exchange membrane 20 interposed between the cathode electrode 14 and the anode electrode 15.
Each cathode chamber 11 is formed with an inlet 111 on an inlet side to receive the cathode reactant A1, and each cathode chamber 11 is formed with an outlet 112 on an outlet side to discharge the cathode mixture B1, with the inlet side and the outlet side being opposite to each other. Each anode chamber 12 is formed with an inlet 121 on an inlet side to receive anode reactant A2, and each anode chamber 12 is formed with an outlet 122 on an outlet side to discharge anode mixture B2, with the inlet side and outlet side being opposite each other.
In some embodiments, the inlets 111 of each cathode chamber 11 are connected to each other by one line for simultaneous injection of the cathode reactant A1, and the inlets 121 of each anode chamber 12 are connected to each other by another line for simultaneous injection of the anode reactant A2. The inlet 111 of the cathode chamber 11 is not in communication with the inlet 121 of the anode chamber 12. Similarly, the outlets 112 of the respective cathode chambers 11 are connected to each other by a line so that the electrolysis products produced by the respective electrolysis units 10 are converged to form the cathode mixture B1. The outlets 122 of the respective anode chambers 12 are connected to each other by another line so that the electrolysis products generated by the respective electrolysis units 10 are converged to form an anode mixture B2. The outlet 112 of the cathode chamber 11 is not in communication with the outlet 122 of the anode chamber 12.
The inlets 111, 121 may be formed at any position of the cathode chamber 11 or the anode chamber 12, and in general, the inlets 111, 121 are formed at a position near the bottom of the cathode chamber 11 or the anode chamber 12. The positions of the outlets 112 and 122 are located at a higher level than the positions of the inlets 111 and 121. For example: the inlets 111, 121 may be formed near the bottom of the electrolysis cell 10, and the outlets 112, 122 may be formed at a position half or more of the height of the electrolysis cell 10. However, the invention is not limited thereto.
Referring to fig. 3, the cathode 14 is disposed on the cathode chamber 11, and a cathode catalyst 141 is formed on a plane of the cathode 14 facing the ion exchange membrane 20 to promote the reduction reaction. The other plane of the cathode electrode 14 is located within the cathode chamber 11 and is in contact with the cathode reactant A1. The anode electrode 15 is disposed on the anode chamber 12, and an anode catalyst 151 is formed on a plane of the anode electrode 15 facing the ion exchange membrane 20 to promote the oxidation reaction. The other plane of the anode electrode 15 is located within the anode chamber 12 and is in contact with the anode reactant A2. An external power source may be applied to the cathode electrode 14 and the anode electrode 15 to perform electrolysis.
In order to avoid contact between the cathode electrode 14 of an electrolysis cell 10 and the anode electrode 15 of an adjacent electrolysis cell 10, an insulating plate 13 is provided between adjacent electrolysis cells 10, which is completely separated. In this way, when a voltage is externally applied to the cathode electrode 14 and the anode electrode 15, it is ensured that the cathode electrode 14 does not contact the anode electrode 15, so as to avoid occurrence of short circuit.
In the present invention, the cathode electrode 14 may have a dense mesh structure, and the material forming the cathode electrode 14 may be a conductive material, such as metal or carbon. The anode electrode 15 may be a dense mesh structure, and the material forming the anode electrode 15 may be a conductive material, such as metal or carbon.
The cathode catalyst 141 may be various metals, metal compounds, alloys, carbon compounds containing at least one of heteroatoms or metals, or any combination thereof. The metal may be vanadium, chromium, manganese, iron, cobalt, nickel, copper, tin, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, iridium, platinum, gold, aluminum, indium, titanium, lead, bismuth, antimony, tellurium, lanthanum, cerium, neodymium, or combinations thereof. The metal compounds include organic metal compounds and inorganic metal compounds, and encompass metal halides, metal oxides, and metal hydroxides. The carbon compound containing at least one of a heteroatom or a metal may be a structure composed of nitrogen-containing graphite, nitrogen-containing graphene, or nitrogen-containing carbon tube and a metal atom.
The anode catalyst 151 may be various metals, metal compounds, alloys, carbon compounds containing at least one of heteroatoms or metals, or any combination thereof. The metal may be vanadium, chromium, manganese, iron, cobalt, nickel, copper, tin, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, iridium, platinum, gold, aluminum, indium, titanium, lead, bismuth, antimony, tellurium, lanthanum, cerium, neodymium, or combinations thereof. The metal compounds include organic metal compounds and inorganic metal compounds, and encompass metal halides, metal oxides, and metal hydroxides. The carbon compound containing at least one of a heteroatom or a metal may be a structure composed of nitrogen-containing graphite, nitrogen-containing graphene, or nitrogen-containing carbon tube and a metal atom.
The ion exchange membrane 20 has a thickness of 10 micrometers to 5000 micrometers, and the ion exchange membrane 20 may be a cation exchange membrane, for example: a cation exchange membrane comprising polyvinylsulfonic acid, fullerene crosslinked polysulfonic acid, polyacrylic acid, or perfluoroethanedisulfonic acid; alternatively, the ion exchange membrane 20 may be an anion exchange membrane, such as: an anion exchange membrane comprising polystyrene methyltrimethylammonium chloride or polyether.
Second embodiment
Referring to fig. 4, a second embodiment of the present invention provides a carbon dioxide electrolysis system, which is similar to the first embodiment, and has the main differences that: the electrolysis system for carbon dioxide of the second embodiment further includes a first liquid treatment unit 7 and a second liquid treatment unit 8.
The first liquid treatment unit 7 is in fluid communication with the first gas-liquid separation unit 4 to receive and suitably treat the catholyte mixture L1. The catholyte mixture L1 is processed by the first liquid processing unit 7 to form a first processing liquid R1, wherein the main component of the first processing liquid R1 is a catholyte E1, so that the first processing liquid R1 can be returned to the electrochemical electrolysis device 1 and recycled as a cathode reactant A1. In a preferred embodiment, the first treatment solution R1 is delivered to the first reactant preparation unit 2, and then to the electrochemical electrolysis device 1 after being appropriately prepared. Specifically, the reflux liquid R1 includes bicarbonate, carbonate, or hydroxide.
The second liquid treatment unit 8 is in fluid communication with the second gas-liquid separation unit 5 to receive and suitably treat the anode liquid mixture L2. The anode liquid mixture L2 is processed by the second liquid processing unit 8 to form a second processing liquid R2, wherein the main component of the second processing liquid R2 is the anolyte E2, so that the second processing liquid R2 can flow back to the electrochemical electrolysis device 1 and be reused as the anode reactant A2. In a preferred embodiment, the second treatment solution R2 is delivered to the second reactant preparation unit 3, and then to the electrochemical electrolysis device 1 after being appropriately prepared.
Third embodiment
Referring to fig. 5 and 6, a third embodiment of the present invention provides a carbon dioxide electrolysis system, which is similar to the first embodiment of the present invention, and the main difference is that: the electrolysis system of carbon dioxide of the third embodiment does not include the first gas-liquid separation unit 4 and the second gas-liquid separation unit 5.
Referring to fig. 6, in the third embodiment, each cathode chamber 11 has two outlets 112A, 112B, and the two outlets 112A, 112B are formed at different height positions. The outlet 112A having a higher level may be used to discharge the cathode gas mixture V1, and the outlet 112B having a lower level may be used to discharge the cathode liquid mixture L1. Each anode chamber 12 has two outlets 112A, 112B, and the two outlets 112A, 112B are formed at different height positions. The outlet 122A with a higher level may be used to discharge the anode gas mixture V2, while the outlet 122B with a lower level may be used to discharge the anode liquid mixture L2. In this way, the use of the first liquid treatment unit 7 and the second liquid treatment unit 8 can be omitted.
It should be noted that, in use, the electrolysis system of carbon dioxide of the third embodiment needs to maintain the liquid levels in the cathode chamber 11 and the anode chamber 12 to be half-full or more than half-full, so as to achieve the effect of distinguishing the cathode gas mixture V1 from the cathode liquid mixture L1 and distinguishing the anode gas mixture V2 from the anode liquid mixture L2.
The electrolysis system of carbon dioxide in the third embodiment has an electrochemical electrolysis apparatus 1, a first reactant preparation unit 2, a second reactant preparation unit 3, and an absorption unit 6 similar to those of the first embodiment except for the first gas-liquid separation unit 4 and the second gas-liquid separation unit 5, and thus will not be described herein.
Fourth embodiment
Referring to fig. 7, a fourth embodiment of the present invention provides a carbon dioxide electrolysis system, which is similar to the third embodiment, and the main difference is that: the electrolysis system of carbon dioxide of the fourth embodiment further comprises a first liquid treatment unit 7 and a second liquid treatment unit 8.
The first liquid treatment unit 7 is in fluid communication with the electrochemical electrolysis device 1 to receive and suitably treat the catholyte mixture L1. The catholyte mixture L1 is processed by the first liquid processing unit 7 to form a first processing liquid R1, wherein the main component of the first processing liquid R1 is a catholyte E1, so that the first processing liquid R1 can be returned to the electrochemical electrolysis device 1 and recycled as a cathode reactant A1. In a preferred embodiment, the first treatment solution R1 is delivered to the first reactant preparation unit 2, and then to the electrochemical electrolysis device 1 after being appropriately prepared.
The second liquid treatment unit 8 is in fluid communication with the electrochemical electrolysis device 1 to receive and suitably treat the anolyte mixture L2. The anode liquid mixture L2 is processed by the second liquid processing unit 8 to form a second processing liquid R2, wherein the main component of the second processing liquid R2 is the anolyte E2, so that the second processing liquid R2 can flow back to the electrochemical electrolysis device 1 and be reused as the anode reactant A2. In a preferred embodiment, the second treatment solution R2 is delivered to the second reactant preparation unit 3, and then to the electrochemical electrolysis device 1 after being appropriately prepared.
Referring to fig. 8, the present invention further provides a method for electrolyzing carbon dioxide, which includes: electrolyzing a cathode reactant and an anode reactant by using an electrochemical electrolysis device to form a cathode mixture and an anode mixture respectively (step S1); treating the cathode mixture with an absorption unit to divide the cathode mixture into a cathode gas product and a reflux (step S2); delivering the reflux liquid to a first reactant preparation unit (step S3); after the first reactant preparation unit receives the reflux liquid, the cathode reactant is supplied to the electrochemical electrolysis apparatus (step S4).
In step S1, the cathode reactant includes carbon dioxide gas and a catholyte, the anode reactant includes an anolyte, the cathode mixture includes carbon monoxide, hydrogen, liquid sodium hydroxide and the catholyte generated by the electrolysis reaction, and the anode mixture includes chlorine and the anolyte. In step S2, the cathode gas product includes carbon monoxide and hydrogen, i.e. synthesis gas. The reflux liquid comprises catholyte, liquid sodium hydroxide and carbon dioxide, so that the reflux liquid can flow back to the electrochemical electrolysis equipment through the steps S3 to S4, and the carbon dioxide conversion rate of the electrolysis method of the carbon dioxide is improved. According to the method, the invention can convert the carbon dioxide into the synthesis gas which can be used as fuel, thereby not only reducing the problem of greenhouse effect, but also providing renewable energy sources.
Advantageous effects of the embodiment
One of the advantages of the present invention is that the electrolysis system and method for carbon dioxide provided by the present invention can decompose greenhouse gas (carbon dioxide) by "the cathode reactant A1 comprises carbon dioxide or carbonate or bicarbonate-containing compound, the cathode mixture B1 comprises carbon monoxide and hydrogen, the anode mixture B1 comprises chlorine" and "the absorption unit 6 processes the cathode mixture B1 and separates a synthesis gas comprising carbon monoxide and hydrogen", and the system and method have the effect of decomposing greenhouse gas (carbon dioxide) and producing synthesis gas (carbon monoxide and hydrogen) which can be used as fuel and alkaline liquid products with commercial use.
Furthermore, the system and method for electrolyzing carbon dioxide of the present invention divide the cathode mixture into a cathode gas product and a reflux liquid by the absorption unit, wherein the cathode gas product comprises the synthesis gas, and the reflux liquid is refluxed to the electrochemical electrolysis device, so that the content of the synthesis gas in the cathode gas product is increased and the cathode gas product can be stably generated in a continuous manner.
The foregoing disclosure is only a preferred embodiment of the present invention and is not intended to limit the scope of the claims, so that all equivalent technical changes made by the application of the present invention and the accompanying drawings are included in the scope of the claims.

Claims (22)

1. An electrolysis system for carbon dioxide, the electrolysis system comprising:
an electrochemical electrolysis device for electrolyzing a cathode reactant and an anode reactant to form a cathode mixture and an anode mixture, respectively; wherein the cathode reactant comprises carbon dioxide or a compound comprising bicarbonate or carbonate, the cathode mixture comprises carbon monoxide and hydrogen, and the anode mixture comprises chlorine; and
an absorption unit in fluid communication with the electrochemical electrolysis apparatus for treating the cathode mixture and separating a synthesis gas comprising the carbon monoxide and the hydrogen.
2. The system of claim 1, wherein the absorption unit separates the cathode mixture into a cathode gas product comprising the synthesis gas and a reflux comprising bicarbonate, carbonate, or hydroxide, which reflux is refluxed to the electrochemical electrolysis device.
3. The electrolysis system of carbon dioxide according to claim 2, further comprising: a first reactant preparation unit in fluid communication between the electrochemical electrolysis device and the absorption unit, the first reactant preparation unit receiving the reflux liquid and providing the cathode reactant to the electrochemical electrolysis device.
4. The electrolysis system of carbon dioxide according to claim 1, wherein the cathode mixture comprises a cathode gas mixture and a cathode liquid mixture, the absorption unit treating the cathode gas mixture.
5. The electrolysis system of carbon dioxide according to claim 1, wherein the catholyte mixture comprises a catholyte mixture comprising metal ions, hydroxide ions or metal hydroxides.
6. The electrolysis system of carbon dioxide according to claim 4, further comprising: the first gas-liquid separation unit is in fluid communication between the electrochemical electrolysis equipment and the absorption unit, and divides the cathode mixture into the cathode gas mixture and the cathode liquid mixture.
7. The electrolysis system of carbon dioxide according to claim 4, further comprising: a first liquid treatment unit in fluid communication with the electrochemical electrolysis device, the first liquid treatment unit treating the catholyte mixture to produce a first treatment liquid, the first treatment liquid being returned to the electrochemical electrolysis device.
8. The electrolysis system of carbon dioxide of claim 7, further comprising: a first reactant preparation unit in fluid communication between the electrochemical electrolysis apparatus and the first liquid treatment unit, the first reactant preparation unit receiving the first treatment liquid and providing the cathode reactant to the electrochemical electrolysis apparatus.
9. The electrolysis system of carbon dioxide of claim 1, wherein the anode mixture comprises an anode gas mixture and an anode liquid mixture.
10. The electrolysis system of carbon dioxide according to claim 9, wherein the electrolysis system of carbon dioxide further comprises: and the second gas-liquid separation unit is in fluid communication with the electrochemical electrolysis equipment and divides the anode mixture into the anode gas mixture and the anode liquid mixture.
11. The electrolysis system of carbon dioxide according to claim 9, wherein the electrolysis system of carbon dioxide further comprises: and a second liquid treatment unit in fluid communication with the electrochemical electrolysis device, the second liquid treatment unit treating the anode liquid mixture to produce a second treatment liquid, the second treatment liquid being returned to the electrochemical electrolysis device.
12. The electrolysis system of carbon dioxide according to claim 11, wherein the electrolysis system of carbon dioxide further comprises: a second reactant preparation unit in fluid communication between the electrochemical electrolysis device and the second liquid treatment unit, the second reactant preparation unit receiving the second treatment liquid and providing the anode reactant to the electrochemical electrolysis device.
13. The electrolysis system of carbon dioxide according to claim 1, wherein the electrochemical electrolysis device comprises a plurality of electrolysis cells; each electrolysis unit comprises a cathode electrode positioned in a cathode cavity, an anode electrode positioned in an anode cavity and an ion exchange membrane clamped between the cathode electrode and the anode electrode.
14. The system of claim 13, wherein the cathode electrode is disposed in the cathode chamber, a cathode catalyst is formed on the cathode electrode, the anode electrode is disposed in the anode chamber, an anode catalyst is formed on the anode electrode, and each two adjacent electrolysis units are separated by an insulating plate; wherein the material of the cathode catalyst comprises iron, cobalt, nickel, copper, ruthenium, rhodium, silver, iridium, platinum, gold, titanium or a carbon compound containing any one of the metals, and the material of the anode catalyst comprises ruthenium, rhodium, iridium, titanium or a metal halide, a metal oxide or a metal hydroxide containing any one of the metals.
15. The electrolysis system of carbon dioxide according to claim 13, wherein the cathode chamber has an inlet for receiving the cathode reactant and an outlet for discharging the cathode mixture, and the anode chamber has an inlet for receiving the anode reactant and an outlet for discharging the anode mixture.
16. The electrolysis system of carbon dioxide according to claim 13, wherein the cathode chamber has an inlet to receive the cathode reactant and two outlets to discharge the cathode mixture, and the anode chamber has an inlet to receive the anode reactant and two outlets to discharge the anode mixture.
17. The system of claim 1, wherein the cathode reactant further comprises a catholyte comprising bicarbonate or carbonate; the anode reactant further comprises an anode electrolyte, wherein the anode electrolyte contains chloride ions.
18. The system for the electrolysis of carbon dioxide according to claim 1, wherein the anolyte comprises salts containing chloride ions.
19. A method of electrolyzing carbon dioxide, the method comprising:
electrolyzing a cathode reactant and an anode reactant by using an electrochemical electrolysis device to form a cathode mixture and an anode mixture respectively; wherein the cathode reactant comprises carbon dioxide or a carbonate or bicarbonate containing compound, the cathode mixture comprises carbon monoxide and hydrogen, and the anode mixture comprises chlorine; and
the cathode mixture is treated using an absorption unit to separate a synthesis gas comprising carbon monoxide and hydrogen.
20. The method of claim 19, wherein after the cathode mixture is treated by the absorption unit, the cathode mixture is separated into a cathode gas product and a reflux, the cathode gas product including the synthesis gas, the reflux including bicarbonate, carbonate, or hydroxide; wherein the method for electrolyzing carbon dioxide further comprises: and refluxing the reflux liquid to the electrochemical electrolysis equipment.
21. The method according to claim 20, wherein the method further comprises: and delivering the reflux liquid to a first reactant preparation unit, wherein the first reactant preparation unit provides the cathode reactant to the electrochemical electrolysis equipment.
22. The method of claim 19, wherein the cathode mixture comprises a cathode gas mixture and a cathode liquid mixture, the cathode liquid mixture comprising metal ions, hydroxide ions, or metal hydroxides.
CN202210166509.8A 2022-01-18 2022-02-23 Electrolysis system and method for carbon dioxide Pending CN116497372A (en)

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