WO2016004802A1 - 一种矿化co2制取碳酸氢钠或碳酸钠对外输出电能的方法及设备 - Google Patents

一种矿化co2制取碳酸氢钠或碳酸钠对外输出电能的方法及设备 Download PDF

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WO2016004802A1
WO2016004802A1 PCT/CN2015/080617 CN2015080617W WO2016004802A1 WO 2016004802 A1 WO2016004802 A1 WO 2016004802A1 CN 2015080617 W CN2015080617 W CN 2015080617W WO 2016004802 A1 WO2016004802 A1 WO 2016004802A1
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cathode
anode
region
reaction
sodium
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French (fr)
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谢和平
王昱飞
刘涛
王金龙
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Sichuan University
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Sichuan University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B5/00—Electrogenerative processes, i.e. processes for producing compounds in which electricity is generated simultaneously
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0693—Treatment of the electrolyte residue, e.g. reconcentrating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to the technical field of CO 2 utilization and emission reduction, and particularly relates to a method and a device for externally supplying electric energy while preparing sodium hydrogencarbonate or sodium carbonate by using CO 2 .
  • the present invention provides a novel CO 2 utilization method: mineralized CO 2 to prepare sodium bicarbonate or sodium carbonate to output electric energy externally, in order to realize the process of utilizing CO 2 in mineralization, not only need not
  • the applied energy instead outputs electrical energy to the outside, and at the same time solves the problems of high energy consumption, complicated process, large environmental pollution and low efficiency existing in the existing soda ash preparation method.
  • CMFC CO 2 mineralized fuel cell
  • Calcium hydroxide Ca(OH) 2 is an important alkaline industrial waste commonly found in carbide slag, steel slag, pulp waste, cement kiln dust and fly ash.
  • the Gibbs free energy of the reaction (1) is -62.75 KJ/mol, but this part of the energy cannot be directly converted into electric energy, and if the above reactants are simply mixed, only calcium carbonate is directly produced. Therefore, we designed a CO 2 mineralized fuel cell based on membrane electrolysis technology.
  • a method for producing carbon dioxide or sodium carbonate by using mineralized CO 2 to output electric energy externally based on the idea of CO 2 mineralization utilization, combined with membrane electrolysis technology, utilizing the acidity of CO 2 and the alkalinity of the reaction solution to promote spontaneous reaction Simultaneously, the separation of the product is carried out, and the energy released by the reaction is converted into electric energy output by the membrane electrolysis device while preparing sodium hydrogencarbonate or sodium carbonate.
  • the anion exchange membrane and the cation exchange membrane are placed in a vessel, and the vessel is divided into three parts of an anode zone, an intermediate zone and a cathode zone, and an alkaline material is added to the liquid in the anode zone.
  • a sodium salt as a raw material for the electrolysis reaction is added to the liquid in the intermediate portion to form an intermediate electrolyte
  • a catholyte is added in the cathode region
  • a positive electrode is connected to form a current path
  • an anion formed by decomposition of the sodium salt in the intermediate electrode electrolyte is formed.
  • the cation in the anolyte combines to form a salt; in the cathode region, CO 2 gas is continuously introduced into the catholyte, and hydrogen ions in the catholyte are reduced to hydrogen on the cathode electrode, and CO 2 conversion into the catholyte
  • bicarbonate sodium bicarbonate is formed with sodium ions, and the potential formed by the difference in pH between the anode and cathode regions is utilized.
  • the electrolysis reaction is carried out, the energy released by the acid-base neutralization reaction in the anode region and the CO 2 mineralization reaction occurring in the cathode region is converted into electric energy by using H 2 as a medium to realize external electricity generation.
  • the sodium hydrogencarbonate produced in the cathode region is removed and filtered to obtain solid sodium hydrogencarbonate, or further dried to obtain solid sodium carbonate.
  • the catholyte is a sodium hydrogen carbonate solution, and the concentration thereof is generally in the range of 0.1 mol/L to 10 mol/L;
  • the intermediate electrode electrolyte is a sodium salt solution, and the concentration thereof is generally The range is 0.0001 mol/L to 10 mol/L.
  • the materials added in the anode zone, the intermediate zone and the cathode zone may be added in the form of a solid or may be added in the form of a solution.
  • the sodium salt preferably added to the intermediate portion is a solution in which the sodium salt is formulated to a concentration of 0.1 mol/L to 10 mol/L and then added to the intermediate portion, and a saturated solution of the sodium salt may be used as the intermediate electrolyte.
  • the anolyte and/or catholyte contains a sodium salt. Adding a small amount of sodium salt to the anolyte and / or catholyte can improve liquid conductivity and achieve better electrochemical results.
  • the total concentration of the dissolved phase including the alkaline material and the sodium salt in the anolyte is generally in the range of 0.0001 mol/L to 10 mol/L, and the total concentration of the dissolved phase in the catholyte is generally 0.0001 mol/L to 10 mol/ L range.
  • the sodium salt is selected from the group consisting of sodium chloride, sodium sulfate, and sodium nitrate.
  • Sodium chloride is preferred; the sodium chloride may be an extract of natural salt lakes, seawater in nature, or a product of an industrial process.
  • the alkaline material added in the anode region is at least one of calcium hydroxide, sodium hydroxide, ammonia water, and potassium hydroxide produced in an industrial production process, or may be Alkaline industrial waste, such as calcium carbide slag, steel slag, pulp waste, cement kiln dust and fly ash, organic waste containing amines (ammonia, ethanolamine, triethylamine, etc.).
  • the anode electrode is selected from a hydrogen diffusion electrode; and the cathode electrode is preferably made by supporting a Pt/C catalyst on the foamed nickel.
  • the Pt loading is generally in the range of 0.1 to 0.5 mg/cm 2 .
  • the anode electrode material is made of carbon fiber
  • the gas diffusion electrode has a surface area of 3.24 cm 2
  • the filling layer on the surface of the base carbon paper is loaded with 1 mg/cm 2 of Pt/C catalyst;
  • the surface area and loading of the foamed nickel electrode acts as a cathode.
  • hydrogen gas generated in the cathode region may be added as a raw material hydrogen to the anode region.
  • the CO 2 gas is bubbled into the cathode region.
  • the CO 2 gas has a volume percent concentration of 10 to 100%.
  • a sodium salt is used as the catholyte for the initial reaction, such as a 1 mol/L NaCl solution.
  • the product produced by the anode-anode reaction is removed in time, such as removing the cathode reaction solution for crystallization and solid-liquid separation.
  • the resulting liquid phase can also be re-entered into the reaction system.
  • saturated NaHCO 3 is used as the catholyte, the CO 2 is not directly introduced into the cathode region, and the cathode is not supplied with CO 2 , and the remaining HCO 3 ⁇ in the solution provides the reaction.
  • H + and become CO 3 2- after a period of reaction, the cathode reaction liquid is removed, and excess CO 2 is continuously introduced into the removed reaction liquid, at which time CO 3 2- will be converted into HCO 3 - ,
  • the solubility of sodium hydrogencarbonate in the solution reaches a maximum, crystals are precipitated, and after solid-liquid separation, the liquid phase is returned to the reaction system for reaction.
  • each reaction zone is first washed with a sodium salt solution to counteract the membrane potential caused by the difference in ion concentration.
  • a voltage of 3 V of 5 min is applied to the two poles of the system before the start of the reaction to completely consume the O 2 attached to the surface of the electrode.
  • parameters such as power and voltage generated by the reaction are detected and recorded in real time by a DC load.
  • the invention also provides a device for extracting carbonic acid sodium or sodium carbonate to produce external electric energy by mineralized CO 2 , comprising an anode region, an intermediate region and a cathode region, wherein the anode region and the intermediate region are separated by an anion exchange membrane, and the middle The region and the cathode region are separated by a cation exchange membrane, the anode region, the intermediate region, and the cathode region are capable of accommodating a corresponding electrolyte, the anode region is provided with an anode electrode, and the cathode region is provided with a cathode electrode, The anode electrode is connected by a circuit, the anode region is provided with a raw material hydrogen inlet, and the cathode region is provided with a CO 2 gas inlet and a product hydrogen outlet.
  • the anode region is for accommodating an anolyte containing an alkaline material
  • the alkaline material is at least one of calcium hydroxide, sodium hydroxide, ammonia, and potassium hydroxide produced in an industrial production process.
  • kind of alkaline material can also be alkaline industrial waste such as carbide slag, steel slag, pulp waste, cement kiln dust and fly ash, organic waste containing amines (ammonia, ethanolamine, triethylamine, etc.).
  • a sodium salt may also be included in the anolyte.
  • the total concentration of the dissolved phase in the anolyte is generally in the range of 0.0001 mol/L to 10 mol/L.
  • the intermediate zone is for containing a sodium salt solution, typically at a concentration ranging from 0.0001 mol/L to 10 mol/L, preferably a saturated solution of the sodium salt solution.
  • the cathode region is for accommodating a catholyte
  • the catholyte is a sodium hydrogen carbonate solution, and the concentration thereof is generally in the range of 0.1 mol/L to 10 mol/L.
  • the catholyte It is a saturated solution of sodium bicarbonate.
  • a sodium salt such as sodium chloride, sodium sulfate, and sodium nitrate may also be included in the catholyte.
  • the total concentration of the dissolved phase in the catholyte is generally in the range of 0.0001 mol/L to 10 mol/L.
  • the anode region, the intermediate portion, and the cathode region are respectively provided with inlets and outlets of respective electrolytes.
  • a hydrogen buffer tank is further provided for collecting hydrogen gas generated in the cathode region.
  • the obtained hydrogen can be used as a raw material hydrogen gas to pass into the anode region, and can also be used for other purposes.
  • the obtained solid phase can be obtained by preparing sodium hydrogencarbonate or sodium carbonate, and the obtained liquid phase can be recycled to the cathode region for recycling.
  • the electrolyte outlet of the cathode zone is connected to the crystallization and solid-liquid separation device by a pipe with a valve. When used, the electrolyte can be periodically collected for crystallization and solid-liquid separation, and can also be continuously extracted for crystallization and solid-liquid separation.
  • the electrolyte obtained at the electrolyte outlet of the intermediate zone may be returned to the intermediate zone for recycling after being supplemented with the sodium salt.
  • the electrolyte obtained at the electrolyte outlet of the anode region can be prepared by concentration and solid-liquid separation.
  • the salt should be.
  • the inlet of the electrolyte of the cathode region is connected to the cathode buffer tank, and the electrolyte is supplied to the cathode region through the buffer tank.
  • the outlet of the electrolyte in the cathode region is connected to the cathode buffer tank, and the reacted electrolyte is returned to the cathode buffer tank for recycling, and the CO 2 gas inlet of the cathode region is disposed on the cathode buffer tank.
  • a solid-liquid separation device is disposed in the cathode buffer tank or at the discharge port thereof.
  • the inlet of the electrolyte of the intermediate zone is connected to the intermediate buffer tank, and the electrolyte is supplied to the intermediate zone through the buffer tank. Further, the outlet of the electrolyte in the intermediate zone is connected to the intermediate buffer tank, and the reacted electrolyte is returned to the intermediate buffer tank for recycling, and the intermediate buffer tank is provided with a sodium salt feed port.
  • the inlet of the electrolyte of the anode region is connected to the anode buffer tank, and the electrolyte is supplied to the anode region through the buffer tank.
  • the device comprises an anode current collecting layer, an anode air chamber plate frame, a hydrogen diffusion electrode, an anode liquid chamber plate frame, an anion exchange film, an intermediate chamber plate frame, a cation exchange film, a cathode chamber plate frame, which are sequentially disposed.
  • a cathode electrode and a cathode current collecting layer are connected by a circuit
  • the anode chamber, the intermediate chamber, and the cathode chamber are capable of accommodating a corresponding electrolyte
  • the anode gas chamber plate is provided with a raw material Hydrogen inlet and outlet
  • the cathode chamber plate frame is provided with a CO 2 gas inlet and a product hydrogen outlet
  • the anode liquid chamber plate frame, the intermediate chamber plate frame and the cathode chamber plate frame are respectively provided with inlet and outlet ports of corresponding electrolytes.
  • an inlet of the electrolyte on the frame of the cathode chamber is connected to the cathode buffer tank, and the electrolyte is supplied into the cathode chamber through the cathode buffer tank.
  • the outlet of the electrolyte on the frame of the cathode chamber is also connected with the cathode buffer tank to form a circulation loop, so that the reacted electrolyte is returned to the cathode buffer tank for recycling, and a CO 2 gas inlet is disposed on the cathode buffer tank.
  • the CO 2 gas inlet on the frame of the original cathode chamber can be closed or used as a carrier gas inlet, and the carrier gas is passed through Conducive to take out the generated hydrogen.
  • the inlet of the electrolyte on the intermediate chamber frame is connected to the intermediate buffer tank, and the electrolyte is supplied to the intermediate chamber through the intermediate buffer tank.
  • the outlet of the electrolyte on the middle chamber plate frame is also connected with the intermediate buffer tank to form a circulation loop, so that the reacted electrolyte is returned to the intermediate buffer tank for recycling, and the intermediate buffer tank is provided with sodium salt. Feeding port.
  • the inlet of the electrolyte on the frame of the anode liquid chamber is connected to the anode buffer tank, and the electrolyte is supplied into the anode liquid chamber through the anode buffer tank.
  • the reacted electrolyte collected at the outlet of the electrolyte on the frame of the anode liquid chamber can be directly discharged as waste liquid, and the reactant can be concentrated and separated for recycling, and can be used for other purposes.
  • the anode electrode material is selected from a hydrogen diffusion electrode; and the cathode electrode is preferably selected from a cathode electrode made of a Pt/C catalyst supported on nickel foam.
  • the Pt/C loading is generally in the range of 0.1 to 0.5 mg/cm 2 .
  • the raw material hydrogen inlet is provided on the anode electrode.
  • a peristaltic pump or other conventional device may be employed to effect flow or circulation of electrolyte in each chamber.
  • the gas diffusion electrode actually has a three-layer structure: a current collecting layer, a carbon cloth, and a catalytic layer.
  • the carbon cloth was loaded with a Pt/C catalyst of 1 mg/cm 2 , and then the carbon cloth was stacked with the titanium mesh of the current collecting layer and pressed at 5 ppm under a condition of 25 ° C for 10 minutes to prepare a gas diffusion electrode.
  • the cathode electrode is prepared by directly spraying a Pt/C catalyst onto a carbon cloth of 80 °C.
  • the Pt/C catalyst preparation method supported on the electrode is divided into the following steps: first, 0.1 g of Pt/C (40% Pt) catalyst is placed in a beaker; then 1 ml of distilled water is added thereto.
  • the method for preparing the externally outputting electric energy by using the mineralized CO 2 to obtain sodium bicarbonate or sodium carbonate is based on the in-depth understanding and research of the electrochemical process by the inventors.
  • potential difference such as the concentration potential formed by the difference in concentration between the anode and cathode; the diffusion potential formed by the diffusion of ions between the anode and the cathode; the oxidation reaction from the cathode and the anode respectively And the reaction potential generated by the reduction reaction, or the potential caused by the difference between the acidity and alkalinity of the solution between the anode and the cathode.
  • ⁇ E -0.059 (pH yin- pH yang ), that is to say, as long as the pH yang >pH is negative , after the circuit is turned on, external power generation can be realized.
  • the present invention mainly utilizes the potential generated by the reaction occurring between the anode and the cathode and the potential generated by the ⁇ pH to realize external power generation.
  • the specific electricity production process is: using the acid-base neutralization reaction occurring in the anode region and the CO 2 reaction occurring in the cathode region as the energy released by the carbonate, and using H 2 as a medium, the energy released by the reaction is converted into electric energy.
  • the potential of the CO 2 power generation device can also be converted, once the current load is connected. After that, the anode and cathode reactions can be realized to realize the generation of sodium hydrogencarbonate while generating electricity.
  • the method for preparing carbon dioxide or sodium carbonate to output electric energy by using the mineralized CO 2 of the present invention applies the membrane electrolysis technology to the field of CO 2 mineralization, and realizes the CO 2 mineralization reaction for the first time without external energy and outputting electric power externally.
  • the separation effect of the mineralized product is obtained by using the separation effect of the membrane to obtain sodium hydrogencarbonate, and the obtained sodium hydrogencarbonate is decomposed by heating to obtain high-purity sodium carbonate, both in the basic method principle and in the specific process method. It is brand new.
  • reaction can be spontaneously carried out while each reaction unit can provide a voltage of about 0.1-0.4V externally, that is, a plurality of CO 2 power generation devices connected in series can perform external work, and can also produce a large amount of high-purity carbonic acid.
  • Sodium hydrogen or sodium carbonate this method has great application prospects.
  • the energy is converted into electric energy, which not only solves the problems of high energy consumption, large waste liquid discharge, low utilization rate of raw materials in the preparation process of sodium bicarbonate or sodium carbonate, but also realizes the overall process of external power generation, breaking through the hydrogen bicarbonate.
  • the sodium or sodium carbonate preparation process must have the inherent concept of energy consumption, and in the true sense, achieve zero energy consumption of the end CO 2 emission reduction.
  • FIG. 1 is a schematic view showing a method for preparing soda ash by utilizing CO 2 mineralization to realize external electricity generation
  • FIG. 2 is a schematic view of a CO 2 mineralized fuel cell according to Embodiment 4 of the present invention.
  • 1 is a gas diffusion electrode (anode electrode); 2 is an anion exchange membrane; 3 is a cation exchange membrane; 4 is a nickel-supported Pt/C electrode (cathode electrode); 5 is a hydrogen buffer tank; a is an anode The collector layer; b is the anode gas chamber plate frame; c is the hydrogen diffusion electrode; d is the anode liquid chamber plate frame; e is the anion exchange membrane (AEM); f is the intermediate chamber plate frame; g is the cation exchange membrane (CEM) ; h is the cathode chamber plate frame; i is the cathode electrode; j is the cathode current collector layer; I is the anode buffer tank; II is the intermediate buffer tank; III is the cathode buffer tank.
  • AEM anion exchange membrane
  • CEM cation exchange membrane
  • FIG. 1 The process of producing soda ash by externally producing electricity by using CO 2 mineralization in this embodiment is shown in FIG. 1 .
  • the cation exchange membrane 3 which allows only cations to permeate in the container and prevents the anion from permeating, allows only anions to permeate, and can prevent cation permeation.
  • the membrane 2 is divided into three regions of an anode region, a middle region, and a cathode region.
  • the CO 2 gas is bubbled into the cathode region from the bottom of the vessel as the casing of the CO 2 power generation device, the hydrogen gas generated by the cathode electrode is collected and entered into the buffer tank 5, and the hydrogen gas from the buffer tank is passed to the gas diffusion electrode for reaction.
  • the electrolysis reaction was carried out for 1 h, and the current density was controlled to be 7 mA/cm 2 .
  • the cell voltage was maintained at 0.15 V.
  • the Ca 2+ concentration eluted after the acid-base reaction occurred in the anode region was utilized.
  • the absorption meter measures and simultaneously conducts a chemical titration test on the concentration of bicarbonate ions generated in the cathode region. By comparison with the theoretical formula, the current efficiency of the sodium hydrogencarbonate produced by the electrolysis process is as high as 89%, and the current of Ca 2+ is generated in the anode region. The efficiency reached 91%.
  • the mineralization process of this embodiment is as shown in FIG.
  • the cation exchange membrane 3 which allows only cations to permeate in the container and prevents the anion from permeating, allows only anions to permeate, and can prevent cation permeation.
  • the membrane 2 is divided into three regions of an anode region, a middle region, and a cathode region. A 1 mol/L aqueous ammonia solution was added to the anode region as an anolyte, a 1 mol/L NaHCO 3 solution was added to the cathode region as a catholyte, and a saturated NaCl solution was added to the intermediate portion.
  • the gas diffusion electrode 1 was used as an anode electrode, and the electrode 4 carrying Pt/C of foamed nickel was used as a cathode electrode.
  • the CO 2 gas is bubbled into the cathode region from the bottom of the vessel as the casing of the CO 2 power generation device, the hydrogen gas generated by the cathode electrode is collected and entered into the buffer tank 5, and the hydrogen gas from the buffer tank is passed to the gas diffusion electrode for reaction.
  • the temperature is 25 ° C
  • the resistance of the applied external load is 0, and the current density of the tank can reach 10 mA/cm 2 .
  • the tank voltage can reach 0.31V, and the maximum output power measured by the CO 2 power generation equipment is 3.2W/m 2 .
  • the mineralization process of this embodiment is as shown in FIG.
  • the cation exchange membrane 3 which allows only cations to permeate in the container and prevents the anion from permeating, allows only anions to permeate, and can prevent cation permeation.
  • the membrane 2 is divided into three regions of an anode region, a middle region, and a cathode region. 1 mol/L of Na(OH) 2 was added to a 1 mol/L NaCl solution to form a mixed solution, which was added to the anode region as an anolyte, and a saturated NaHCO 3 solution was added to the cathode region as a catholyte in the middle.
  • a saturated NaCl solution was added to the zone.
  • the gas diffusion electrode 1 was used as an anode electrode, and the electrode 4 carrying Pt/C of foamed nickel was used as a cathode electrode.
  • the CO 2 gas is bubbled into the cathode region from the bottom of the vessel as the casing of the CO 2 power generation device, the hydrogen gas generated by the cathode electrode is collected and entered into the buffer tank 5, and the hydrogen gas from the buffer tank is passed to the gas diffusion electrode for reaction.
  • the temperature is 25 °C
  • the resistance of the applied load is controlled to be 0.
  • the current density at this time can be stably maintained at 12 mA/cm 2 , and the electrolytic reaction is carried out for 1 hour under the conditions, and the sodium hydrogencarbonate formed after the electrolytic reaction 1 is simultaneously
  • the mass of sodium carbonate obtained after cooling, filtering and drying at 110 ° C is 0.210 g.
  • the theoretical value of the current efficiency of Faraday is 0.237 g of sodium carbonate, and the conversion rate of sodium carbonate is as high as 88.6%.
  • the output power is 3.3 W/m 2 .
  • the solution in the anode region is subjected to acid-base titration to test the amount of NaOH consumed, and the carbonate ion generated in the cathode region is subjected to a chemical titration test.
  • the current efficiency of producing sodium hydrogencarbonate is as high as 93. %, while the current efficiency of the acid-base reaction in the anode region reaches 96%.
  • a CO 2 mineralized fuel cell comprises an anode current collecting layer, an anode gas chamber plate frame, a hydrogen diffusion electrode, an anode liquid chamber plate frame, an anion exchange membrane, an intermediate chamber plate frame, and a cation.
  • the exchange membrane, the cathode chamber plate frame, the cathode electrode and the cathode current collecting layer, the anode current collecting layer and the cathode current collecting layer are connected by a circuit, and the anode gas chamber plate frame is provided with a raw material hydrogen inlet and outlet, and the cathode chamber plate frame a carrier gas inlet (which may also close the inlet) and a product hydrogen outlet, wherein the anode liquid chamber plate frame, the intermediate chamber plate frame and the cathode chamber plate frame are respectively provided with inlet and outlet ports of respective electrolytes;
  • the inlet of the electrolyte on the plate frame is connected to the cathode buffer tank, and the outlet of the electrolyte on the frame of the cathode chamber is also connected with the cathode buffer tank to form a circulation loop, and the electrolyte after the reaction is returned to the cathode buffer tank for recycling.
  • CO 2 gas inlet is provided in the buffer tank on the cathode, and the cathode buffer tank provided at the discharge port or a solid-liquid separator; electrolyte inlet on said intermediate plate and frame buffer tank is connected to the intermediate chamber, The buffer tank supplies electrolyte to the intermediate zone, and the electrolyte outlet on the intermediate chamber plate frame is connected to the intermediate buffer tank, so that the reacted electrolyte is returned to the intermediate buffer tank for recycling, and the intermediate buffer tank is disposed at the same time.
  • an electrolyte inlet on the frame of the anode liquid chamber is connected to the anode buffer tank, and an electrolyte is supplied to the anode region through the buffer tank, and the electrolyte outlet on the frame of the anode liquid chamber can be concentrated
  • the separation devices are connected, and the electrolytes in the three liquid chambers (anode liquid chamber, intermediate chamber, and cathode chamber) are respectively flowed or circulated by driving of the peristaltic pump.
  • An H 2 cylinder is connected to the anode side of the device to supply a hydrogen source to the gas diffusion electrode, and hydrogen gas is introduced from the anode inlet and the outlet port.
  • An external buffer tank on the cathode side is connected to a CO 2 cylinder. Both the yin and the yang use stainless steel mesh as the current collector layer.
  • the gas diffusion electrode actually has a three-layer structure: a current collecting layer, a carbon cloth, and a catalytic layer.
  • a 1 g/cm 2 Pt catalyst (Shanghai Hesen Electric Co., Ltd.) was loaded on the carbon cloth having the leveling layer. Subsequently, the carbon cloth was stacked with the titanium mesh of the current collecting layer and pressed at 5 ppm under a condition of 25 ° C for 10 minutes to prepare a gas diffusion electrode.
  • a Pt/C catalyst having the same loading amount (1 mg/cm 2 ) as that of the anode having the same surface area was dried at 60 ° C for 2 hours, and finally pressed at a pressure of 3 MP for 10 minutes to prepare a cathode electrode.
  • the anode and cathode electrodes are each loaded with a Pt/C catalyst by spraying a suspension, and the Pt/C catalyst suspension is prepared as follows: First, 0.1 g of Pt/C (40% Pt) catalyst is placed. a beaker; then 1 ml of distilled water, 4 ml of absolute ethanol and 4.5 g of a perfluorosulfonic acid solution were added thereto, wherein ethanol and perfluorosulfonic acid were respectively dispersed and bonded; the mixture was ultrasonicated to obtain a black suspension. Can be used for spraying.
  • the preparation of the cathode electrode is divided into the following steps: first, 0.1 g of Pt/C (40% Pt) catalyst is placed in a beaker; then 1 ml of distilled water, 4 ml of absolute ethanol and 4.5 g of Nafion solution are added thereto, wherein Ethanol and Nafion acted as dispersing and bonding, respectively; the mixture was sonicated to give a black suspension sprayed onto carbon paper at 80 ° C so that the loading of Pt/C on the carbon paper was 1 mg/cm 2 . Dry at 60 ° C for 2 h, and finally press at 3MP for 10 min.
  • the rate at which the cathode buffer tank is passed through CO 2 is controlled at 10 to 20 ml/min.
  • the liquid flow between the external circulation and the reaction chamber was controlled at 15 ml/min throughout the experiment to ensure the stability of the entire system.
  • An electronic load (ItechIT8511) is connected between the cathode and anode of the system. Immediately after the start of the reaction, current generation can be detected, and the output voltage and output power density can be controlled by adjusting the load size.
  • the representative reaction of the anode in the system is Ca(OH) 2 +H 2 +2Cl - ⁇ CaCl 2 +2H 2 O+2e - , and the cathode passes the reaction 2CO 2 +2H 2 O+2e - +2Na + ⁇ 2NaHCO 3 +H 2 Generate NaHCO 3 .
  • the cathode side HCO 3 - concentration change was measured quantitatively every 30 minutes at a current density of 2.5 A/m 2 .
  • a linear increase in HCO 3 - concentration indicates the continued formation of sodium bicarbonate in the catholyte.
  • the average current efficiency (percentage of electrons entering the NaHCO 3 product) to produce NaHCO 3 was calculated to be 91.4%.
  • the change in the concentration of chloride ions on the anode side was measured by ion chromatography to determine the amount of CaCl 2 produced on the anode side.
  • the linear increase in chloride ion content was in line with expectations, and the average current efficiency for generating CaCl 2 in 120 min was calculated to be 93.4%.
  • Equation 1 should not have a net stoichiometric formation and consumption of H 2 .
  • the solubility of NaHCO 3 in the solution was determined by acid-base neutralization titration: 0.5 ml from the cathode was transferred to the Erlenmeyer flask every half hour, and 3 drops of methyl red-bromocresol green indicator were added and added. Appropriate amount of distilled water, the solution was bright green, and then the solution was titrated to dark red with HCl at a concentration of 0.0011 mol/L. In order to avoid the influence of Na 2 CO 3 in the experiment, a phenolphthalein indicator was added to the control group.
  • the content of Na + was determined by atomic absorption spectroscopy, and the content of Cl - was determined by ion chromatography. According to the experimental results, it is known that CaCl 2 is formed at the anode and NaHCO 3 is formed at the cathode.
  • Example 4 The test was carried out using the same equipment and operating procedures as in Example 4. The only difference is that when the electricity production process is stable, 10 ml/min of N 2 is used instead of CO 2 to pass into the cathode reaction buffer tank. Subsequently, the output voltage and output power density gradually decrease and eventually drop to zero. At this point, the CO 2 is replaced by N 2 into the cathode buffer tank, and the system immediately generates voltage and current again. During the entire process, the output voltage and power were recorded every 60 s, and the change in pH at the cathode side was measured. The results show that when the system is introduced with CO 2 , the generated H 2 CO 3 causes the cathode pH to decrease, which is accompanied by the generation of electric energy.
  • H + in the solution will be insufficient to capture electrons generated at the anode.
  • H 2 O will act as an electron acceptor, generating H 2 while producing OH ⁇ . This will cause an increase in pH and the production process will gradually stop.
  • Example 4 The test was carried out using the same equipment and operating procedures as in Example 4. The only difference was the addition of 1 ml of a saturated Ca(OH) 2 solution to the anode during the initial stages of the reaction. As the electricity generation process progresses, the Ca(OH) 2 of the anode is gradually consumed, and the output voltage and power density gradually decrease and eventually become zero. Subsequently, 1 ml of a saturated Ca(OH) 2 solution was again added to the anode, and the system again outputted electric energy.
  • Example 4 Using the apparatus described in Example 4, the experiment the anode was added Ca (OH) 2, intermediate pole saturated NaCl solution, the cathode saturated NaHCO 3 solution, the reaction to the beginning of the CO 2 barrier, without the cathode of CO 2 Upon entry, at an energy density of 30.86 A/m 2 , the remaining HCO 3 - in the solution will provide H + for the reaction and become CO 3 2- .
  • the output energy density will gradually decrease from 3.55 W/m 2 to 2.96 W/m 2 ; at this time, an excess of CO 2 is introduced into the cathode buffer tank, in the process, CO 3 2- will Conversion to HCO 3 - , when the solubility of sodium bicarbonate in the solution reaches a maximum, crystals will be precipitated.
  • the solid phase can be used to prepare sodium bicarbonate or sodium carbonate, and the liquid phase returns to the CMFC battery system, and the energy is immediately output. It rises back to 3.55 W/m 2 and cycles through it to sustainably produce electricity and sodium bicarbonate or sodium carbonate.
  • the stability of the CMFC system was examined in the study.
  • 300 ml of a 1 mol/L NaCl solution was added to the cathode and the anode of the system, and 300 ml of a saturated NaCl solution was added to the intermediate chamber.
  • an appropriate amount of calcium carbide slag was added to the anode, and a certain flow of CO 2 was introduced into the catholyte.
  • the fixed current density is 30.86 A/m 2 , and the system is continuously operated for 17 h or more. During this period, the output power is measured every 2 min. The results show that the system has good stability.
  • the concentration of CO 2 in the flue gas emitted by thermal power plants is generally low (usually ⁇ 20%).
  • mixed N 2 /CO 2 is used to investigate the CO 2 concentration.
  • the impact of the electricity production process 50 ml of 1 mol/L NaCl solution was added to each of the anode and cathode regions, and 50 ml of saturated NaCl solution was added to the intermediate chamber.
  • different concentrations (10%, 20%, 50%, 100%) of CO 2 were introduced into the cathode electrolyte.
  • the gas was mixed at a gas velocity of 100 ml/min. Wherein by adjusting the concentration of CO 2 and N 2 flow rate of CO 2 is controlled.

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Abstract

公开了一种矿化CO2制取碳酸氢钠或碳酸钠对外输出电能的方法及设备，所述设备包括阳极区、中间区、阴极区，阳极区与中间区之间通过阴离子交换膜（2）隔开，中间区与阴极区之间通过阳离子交换膜（3）隔开，所述阳极区、中间区、阴极区能够容纳对应的电解液，所述阳极区设置有阳极电极（1），所述阴极区设置有阴极电极（4），阴、阳电极通过电路连接，阳极区设置有原料氢气入口，阴极区设置有CO2气体入口和产品氢气出口。所述方法基于CO2矿化利用的思想，结合膜电解技术，利用CO2所具有的酸性和反应溶液的碱性促使反应自发进行的同时实现产物的分离，在制取碳酸氢钠或碳酸钠的同时将反应释放的能量通过膜电解装置转换为电能输出。所述方法及设备在低能耗、原料利用率高、环境污染小的情况下制取纯碱的同时对外输出电能。

Description

一种矿化CO2制取碳酸氢钠或碳酸钠对外输出电能的方法及设备 技术领域
本发明涉及CO2利用减排技术领域，特别涉及一种在利用CO2制取碳酸氢钠或碳酸钠的同时对外提供电能的方法和设备。
技术背景
自工业革命以来，人类活动排放的以CO2为主的温室气体已成为影响全球气候变化的主要因素。预计到2015年之前二氧化碳排放量的年均增长率为5.4％，2015年到2030年期间为3.3％，2030年中国的排放量将达到114亿吨，减少CO2排放已成为全球的共识。但据估计2005年到2030年间，煤、石油、天然气等化石燃料仍将是一次能源的主要来源，并在能源需求增长总量中占到84％，乐观估计到2035年全球CO2排放量也将达到354亿吨，化石燃料消耗产生的CO2将持续增长。
到目前为止，人们普遍认为煤、石油等化石燃料转变为CO2便是能量释放的终点，同时普遍认为处理CO2是一个耗能的化学过程，因此，许多关于CO2矿化的研究都致力于降低反应能耗，提高产物的附加值来实现矿化CO2的经济可行性。然而几乎所有研究者都忽略了理论上从CO2转变为更稳定的碳酸盐，其过程的△G<0，这意味着矿化过程是可以自发进行并有能量释放的。如果能够获取CO2矿化过程中所释放的化学能，便有可能实现一种能量输出而不是能量消耗的CO2减排利用方法。通常情况下，矿化反应是放热反应，之前已经有研究提出我们可以回收这部分反应热，但是由于热能回收的效率问题，该方法的实施有待商榷。
发明内容
针对上述问题，本发明提供了一种全新的CO2利用方法：矿化CO2制取碳酸氢钠或碳酸钠对外输出电能的方法，以期实现在矿化利用CO2的过程中，不仅不需外加能量反而对外输出电能，同时解决现有纯碱制取方法存在的高能耗、工艺过程复杂、环境污染大、效率低等诸多问题。我们设计了一套CO2矿化燃料电池(CMFC)，通过重置电解过程来实现CO2的有效利用。氢氧化钙Ca(OH)2是一种重要的碱性工业废料，常存在于电石渣、钢渣、纸浆废料、水泥窑灰和粉煤灰中。在现有CO2矿化利用的研究中，氢氧化钙被直接拿来与CO2反应生成碳酸钙。碳酸钙是一种重要的工业原料，但其在自然界中的储量已经过剩。然而碳酸氢钠(NaHCO3)——生产碳酸钠、碳酸氢钠、碳酸镁等产品的重要原料，在工业上严重短缺。因此，我们将NaCl引入反应体系中以期能够生成碳酸氢钠来取代碳酸钙。最终，以CO2矿化反应为原型我 们实现了反应(1)：
2CO2+Ca(OH)2+2NaCl→2NaHCO3+CaCl2。。。。。。ΔGf 0＝-62.75kJ/mol   (式1)
反应(1)的吉布斯自由能是-62.75KJ/mol，但是这部分能量不能够直接转化为电能，另外，如果将上述反应物简单地混合只会直接生成碳酸钙。因此，我们基于膜电解技术设计了一个CO2矿化燃料电池。
本发明通过以下技术方案来实现：
一种矿化CO2制取碳酸氢钠或碳酸钠对外输出电能的方法，基于CO2矿化利用的思想，结合膜电解技术，利用CO2所具有的酸性和反应溶液的碱性促使反应自发进行的同时实现产物的分离，在制取碳酸氢钠或碳酸钠的同时将反应释放的能量通过膜电解装置转换为电能输出。
作为可选方式，在上述方法中，将阴离子交换膜和阳离子交换膜置于容器中，将容器分隔为阳极区、中间区和阴极区三个部分，在阳极区的液体中加入碱性物料构成阳极电解液，在中间区液体中加入作为电解反应原料的钠盐构成中间电解液，在阴极区加入阴极电解液，连接阴阳电极形成电流通路，中间极电解液中的钠盐分解形成的阴离子和钠离子在电流作用下分别通过阴离子交换膜和阳离子交换膜进入到阳极区和阴极区，在阳极区，氢气在阳极电极上氧化生成的氢离子与加入的碱性物料发生中和反应，阴离子与阳极电解液中的阳离子结合生成盐；在阴极区，向阴极电解液中持续通入CO2气体，阴极电解液中的氢离子在阴极电极上还原为氢气，进入阴极电解液中的CO2转化为碳酸氢根，与钠离子生成碳酸氢钠，利用阴阳极区之间pH值之差形成的电势，在电解反应进行时，阳极区发生的酸碱中和反应和阴极区发生的CO2矿化反应所释放的能量以H2作为媒介转变为电能实现对外产电。
作为可选方式，在上述方法中，反应完成后将阴极区产生的碳酸氢钠移出经过滤得到固体碳酸氢钠，或进一步烘干得到固体碳酸钠。
作为可选方式，在上述方法中，所述阴极电解液为碳酸氢钠溶液，其浓度一般在0.1mol/L～10mol/L范围；所述中间极电解液为钠盐溶液，其浓度一般在0.0001mol/L～10mol/L范围。在阳极区、中间区和阴极区加入的物料，均可以固体的形式加入，也可以溶液的形式加入。中间区优选加入的钠盐是将钠盐配制成0.1mol/L～10mol/L浓度的溶液再加入到中间区，也可采用钠盐的饱和溶液作为中间电解液。
作为可选方式，在上述方法中，所述阳极电解液和\或阴极电解液中含有钠盐。在阳极电解液和\或阴极电解液中加入少量钠盐可以提高液体导电性，取得更好的电化学效果。作为可 选，所述阳极电解液中包括碱性物料和钠盐在内的溶解相总浓度一般在0.0001mol/L～10mol/L范围，阴极电解液溶解相总浓度一般在0.0001mol/L～10mol/L范围。
作为可选方式，在上述方法中，所述钠盐选自氯化钠、硫酸钠和硝酸钠。优选氯化钠；所述氯化钠可以是自然界中天然的盐湖、海水的提取物，也可以是工业生产过程的产物。
作为可选方式，在上述方法中，所述阳极区加入的碱性物料为工业生产过程中所产生的含有氢氧化钙、氢氧化钠、氨水、氢氧化钾中的至少一种，也可以是碱性工业废料，如电石渣、钢渣、纸浆废料、水泥窑灰和粉煤灰、包含胺类的有机废物(氨水、乙醇胺、三乙胺等)等。
作为可选方式，在上述方法中，所述阳极电极选用氢气扩散电极；所述阴极电极优先考虑选用在泡沫镍上担载Pt/C催化剂制成。所述Pt担载量一般在0.1-0.5mg/cm2范围。
作为可选方式，所述阳极电极材料碳纤维制成的气体扩散电极，表面积为3.24cm2，其基底碳纸表面的填平层上担载有1mg/cm2的Pt/C催化剂；采用具有相同表面积和负载量的泡沫镍电极作为阴极。
作为可选方式，在上述方法中，可以将阴极区产生的氢气作为原料氢气加入阳极区。
作为可选方式，在上述方法中，所述CO2气体以鼓泡的方式通入到阴极区。
作为可选方式，在上述方法中，所述CO2气体的体积百分浓度为10～100％。
作为可选方式，在上述方法中，采用钠盐作为最初反应的阴极电解液，如采用1mol/L的NaCl溶液。
作为可选方式，在上述方法中，及时将阴阳极反应产生的产物移出，如将阴极反应液移出进行结晶和固液分离。所得液相还可重新进入反应体系。
作为可选方式，在上述方法中，使用饱和的NaHCO3作阴极电解液，在阴极区域不直接通入CO2，阴极没有了CO2的通入，溶液中剩余的HCO3 -会为反应提供H+并变成CO3 2-，反应一段时间后，将阴极反应液移出，再向被移出的反应液中持续通入过量的CO2，此时CO3 2-将转化为HCO3 -，当碳酸氢钠在溶液中的溶解度达到最大值后将析出晶体，固液分离后，液相重新返回反应体系进行反应。
作为可选方式，在上述方法中，首先采用钠盐溶液来清洗各反应区域，来抵消离子浓度差异引起的膜电位。
作为可选方式，在上述方法中，反应开始前在系统两极施加5min的3V的电压来彻底消耗掉电极表面附着的O2。
在本发明的上述技术方案中，反应产生的功率、电压等参数通过直流负载进行实时检测和记录。
本发明还提供了一种矿化CO2制取碳酸氢钠或碳酸钠对外输出电能的设备，包括阳极区、中间区、阴极区，阳极区与中间区之间通过阴离子交换膜隔开，中间区与阴极区之间通过阳离子交换膜隔开，所述阳极区、中间区、阴极区能够容纳对应的电解液，所述阳极区设置有阳极电极,所述阴极区设置有阴极电极，阴、阳电极通过电路连接，阳极区设置有原料氢气入口，阴极区设置有CO2气体入口和产品氢气出口。
作为可选方式，所述阳极区用于容纳含有碱性物料的阳极电解液，碱性物料为工业生产过程中所产生的含有氢氧化钙、氢氧化钠、氨水、氢氧化钾中的至少一种的碱性物料。也可以是碱性工业废料，如电石渣、钢渣、纸浆废料、水泥窑灰和粉煤灰、包含胺类的有机废物(氨水、乙醇胺、三乙胺等)等。所述阳极电解液中还可以包含钠盐。所述阳极电解液中的溶解相总浓度一般在0.0001mol/L～10mol/L范围。
作为可选方式，所述中间区用于容纳钠盐溶液，其浓度一般在0.0001mol/L～10mol/L范围，优选钠盐溶液的饱和溶液。
作为可选方式，所述阴极区用于容纳阴极电解液，所述阴极电解液为碳酸氢钠溶液，其浓度一般在0.1mol/L～10mol/L范围，作为可选，所述阴极电解液为碳酸氢钠饱和溶液。所述阴极电解液中还可以包含钠盐(如氯化钠、硫酸钠和硝酸钠)。所述阴极电解液中的溶解相总浓度一般在0.0001mol/L～10mol/L范围。
作为可选方式，在上述设备中，所述阳极区、中间区和阴极区分别设置有相应电解液的入口和出口。
作为可选方式，在上述设备中，还设置有氢气缓冲罐，用于收集存储阴极区产出的氢气。所得氢气可作为原料氢气通入阳极区，也可用于其他用途。
作为可选方式，所述阴极区的电解液出口获得的电解液经浓缩和固液分离后，所得固相可制取碳酸氢钠或碳酸钠，所得液相可回到阴极区循环使用。所述阴极区的电解液出口采用带阀门的管道与结晶和固液分离装置相连，使用时可定期采出电解液进行结晶和固液分离，也可以持续采出进行结晶和固液分离。
作为可选方式，所述中间区的电解液出口获得的电解液经补充钠盐后可回到中间区循环使用。
作为可选方式，所述阳极区的电解液出口获得的电解液经浓缩和固液分离后也可制取相 应的盐。
作为可选方式，在上述设备中，所述阴极区的电解液的入口与阴极缓冲罐相连，通过缓冲罐向阴极区供给电解液。进一步的，所述阴极区的电解液的出口与阴极缓冲罐相连，使反应后的电解液回到阴极缓冲罐中循环使用，同时将所述阴极区的CO2气体入口设置在阴极缓冲罐上，并在所述阴极缓冲罐中或其出料口处设置固液分离装置。
作为可选方式，在上述设备中，所述中间区的电解液的入口与中间缓冲罐相连，通过缓冲罐向中间区供给电解液。进一步的，所述中间区的电解液的出口与中间缓冲罐相连，使反应后的电解液回到中间缓冲罐中循环使用，同时所述中间缓冲罐上设置有钠盐给料口。
作为可选方式，在上述设备中，所述阳极区的电解液的入口与阳极缓冲罐相连，通过缓冲罐向阳极区供给电解液。
作为可选方式，所述设备包括依次设置的阳极集流层、阳极气室板框、氢气扩散电极、阳极液体室板框、阴离子交换膜、中间室板框、阳离子交换膜、阴极室板框、阴极电极和阴极集流层，阳极集流层和阴极集流层通过电路连接，所述阳极室、中间室、阴极室能够容纳对应的电解液，所述阳极气室板框上设置有原料氢气进出口，所述阴极室板框上设置有CO2气体入口和产品氢气出口，所述阳极液体室板框、中间室板框和阴极室板框上分别设置有相应电解液的进出口。进一步的，所述阴极室板框上电解液的入口与阴极缓冲罐相连，通过阴极缓冲罐向阴极室中供应电解液。进一步的，所述阴极室板框上电解液的出口也与阴极缓冲罐相连形成循环回路，使反应后的电解液回到阴极缓冲罐中循环使用，同时在阴极缓冲罐上设置CO2气体入口，并在所述阴极缓冲罐中或其出料口处设置固液分离装置，此时可封闭原阴极室板框上的CO2气体入口或将其作为载气入口，通过通入载气有利于将生成的氢气带出。
作为可选方式，在上述设备中，所述中间室板框上电解液的入口与中间缓冲罐相连，通过中间缓冲罐向中间室中供应电解液。进一步的，所述中间室板框上电解液的出口也与中间缓冲罐相连形成循环回路，使反应后的电解液回到中间缓冲罐中循环使用，同时所述中间缓冲罐上设置有钠盐给料口。
作为可选方式，在上述设备中，所述阳极液体室板框上电解液的入口与阳极缓冲罐相连，通过阳极缓冲罐向阳极液体室中供应电解液。阳极液体室板框上电解液的出口处采出的反应后的电解液可直接作为废液排放，也可将反应物浓缩分离后回收利用，还可以用做其他用途。
作为可选方式，在上述设备中，所述阳极电极材料选用氢气扩散电极；所述阴极电极优先考虑选用在泡沫镍上担载Pt/C催化剂制成的阴极电极。所述Pt/C担载量一般在 0.1-0.5mg/cm2范围。
作为可选方式，在上述设备中，所述原料氢气入口设置在阳极电极上。
作为可选方式，可以采用蠕动泵或其他常用设备来实现各腔室中电解液的流动或循环。
作为可选方式，在上述设备中，所述阳极电极采用的氢气扩散电极的表面积为3.24cm2，其基底碳纸表面负载1mg/cm2的Pt/C催化剂；采用具有相同表面积和负载量的以Pt/C为催化剂的电极作为阴极。
作为可选方式，在上述设备中，气体扩散电极实际上有三层结构：集流层、碳布和催化层。碳布上负载1mg/cm2的Pt/C催化剂，随后将碳布与集流层的钛网叠放在一起在5MP、25℃的条件下压制10min，从而制得气体扩散电极。
作为可选方式，在上述设备中，阴极电极为Pt/C催化剂直接喷涂到80℃的碳布上制得。
作为可选方式，在上述设备中，电极上负载的Pt/C催化剂制备方法分为以下几个步骤：首先取0.1g Pt/C(40％Pt)催化剂置于烧杯；随后向其中加入1ml蒸馏水、4ml无水乙醇和4.5g的全氟磺酸(Nafion)溶液，其中乙醇和全氟磺酸分别起分散和粘合的作用，将上述混合溶液超声两小时后备用；将上述混合物超声后得到黑色的悬浮液喷涂到80℃的碳纸上，使碳纸上Pt/C的负载量为1mg/cm2；在60℃下干燥2h，最后在3MP的压力下压制10min，将负载有催化剂的碳纸压制到导电材料(如石墨、钛等)上即可。
在本发明的上述技术方案中，利用阴极产生的氢气作为阳极气体扩散电极的氢气来源，且阳极区的含碱性的溶液为仅含氢氧化钙的溶液时，利用CO2的矿化实现氯化钠制取纯碱的同时对外产电的总反应如反应式1。
本发明提出的矿化CO2制取碳酸氢钠或碳酸钠对外输出电能的方法，是基于发明人对电化学过程深刻理解和研究所完成的。在电化学过程中，众多因素均会引起电势差，如阴阳极之间溶液的浓度差所形成的浓差电势；阴阳极之间离子扩散所形成的扩散电势；由阴极和阳极分别发生的氧化反应和还原反应所产生的反应电势，或由阴阳极之间溶液的酸碱性之差引起的电势。根据理论公式ΔE＝-0.059(pH阴-pH阳)，也就是说只要pH阳>pH阴，导通电路后，便能实现对外产电。本发明主要是利用阴阳极之间发生的反应所产生的电势和ΔpH所产生的电势实现对外产电。具体产电的过程是：利用阳极区发生的酸碱中和反应和阴极区发生的CO2反应为碳酸盐所释放的能量，以H2作为媒介，实现将反应释放的能量转变为电能，同时由于阳极区加入的碱性物料和在阴极区不断通入CO2后形成的碳酸盐之间具有较大的pH之差，也可以转变为CO2发电装置的电势，一旦接入电流负载后，便能实现阴、阳极反应实现 产生碳酸氢钠的同时对外发电。
本发明提出的矿化CO2制取碳酸氢钠或碳酸钠对外输出电能的方法，将膜电解技术运用到CO2矿化领域，首次实现CO2矿化反应不需要外加能量而对外输出电功，同时利用膜具有的分离效果实现矿化产物的隔离从而得到碳酸氢钠，所得到的碳酸氢钠经加热分解后制取高纯碳酸钠，无论在基本方法原理上还是在具体工艺方法上都是全新的。在常温条件下，反应自发进行的同时每个反应单元能对外提供大约0.1-0.4V的电压，也就是说多个串联的CO2发电设备可对外做功，同时还能产出大量的高纯碳酸氢钠或碳酸钠，该方法具有巨大的应用前景。
本发明所提出的矿化CO2制取碳酸氢钠或碳酸钠对外输出电能的方法，其在将CO2矿化为高附加值的碳酸氢钠或碳酸钠的同时，将矿化反应所释放的能量转变为电能，不仅解决了碳酸氢钠或碳酸钠制备过程存在的能耗高、废液排放量大、原料利用率低等问题，还实现了整体过程对外发电，突破了人们对碳酸氢钠或碳酸钠制备过程必然存在能量消耗的固有观念，而且真正意义上实现了末端CO2减排的零能耗。
附图说明：
图1为利用CO2矿化实现对外产电的同时制取纯碱的方法示意图；
图2为本发明实施例4所述的CO2矿化燃料电池的示意图；
图标记：1为气体扩散电极(阳极电极)；2为阴离子交换膜；3为阳离子交换膜；4为泡沫镍担载Pt/C的电极(阴极电极)；5为氢气缓冲罐；a为阳极集流层；b为阳极气室板框；c为氢气扩散电极；d为阳极液体室板框；e为阴离子交换膜(AEM)；f为中间室板框；g为阳离子交换膜(CEM)；h为阴极室板框；i为阴极电极；j为阴极集流层；I为阳极缓冲罐；II为中间缓冲罐；III为阴极缓冲罐。
具体实施方式：
以下通过实施例的具体实施方式再对本发明的上述内容作进一步的详细说明。但不应当将此理解为本发明上述主题的范围仅限于以下的实例。在不脱离本发明的精神和原则之内做的任何修改，以及根据本领域普通技术知识和惯用手段做出的等同替换或者改进，均应包括在本发明的保护范围内。
实施例1
本实施例利用CO2矿化实现对外产电制取纯碱的工艺过程如图1所示。在作为CO2发电设备壳体的容器中，由设置在容器内只允许阳离子透过、而能阻止阴离子透过的阳离子交换膜3，只允许阴离子透过、而能阻止阳离子透过的阴离子交换膜2分隔为阳极区、中间区、 阴极区三个区域。在1mol/L的NaCl溶液中加入氢氧化钙固体形成含饱和Ca(OH)2的浑浊溶液，加入至阳极区中作为阳极电解液，加入0.3mol/L的NaHCO3溶液至阴极区中作为阴极电解液，在中间区加入6mol/L的NaCl溶液作为中间电解液。采用气体扩散电极1作为阳极电极，采用泡沫镍担载Pt/C的电极4作为阴极电极。将CO2气体从作为CO2发电设备壳体的容器底部鼓泡通入阴极区，将阴极电极产生的氢气收集并进入缓冲罐5，来自缓冲罐中的氢气通入气体扩散电极进行反应，在温度为25℃下，进行电解反应1h，控制电流密度为7mA/cm2，此时槽电压能维持在0.15V，反应完成后，对阳极区发生酸碱反应后溶出的Ca2+浓度利用原子吸收仪测定，同时对阴极区产生的碳酸氢根离子浓度进行化学滴定测试，通过与理论公式的对比，电解过程产生碳酸氢钠的电流效率高达89％，同时在阳极区生成Ca2+的电流效率达到91％。
实施例2
本实施例的矿化过程如附图1所示。在作为CO2发电设备壳体的容器中，由设置在容器内只允许阳离子透过、而能阻止阴离子透过的阳离子交换膜3，只允许阴离子透过、而能阻止阳离子透过的阴离子交换膜2分隔为阳极区、中间区、阴极区三个区域。加入1mol/L的氨水溶液至阳极区中作为阳极电解液，加入1mol/L的NaHCO3溶液至阴极区中作为阴极电解液，在中间区加入饱和的NaCl溶液。采用气体扩散电极1作为阳极电极，采用泡沫镍担载Pt/C的电极4作为阴极电极。将CO2气体从作为CO2发电设备壳体的容器底部鼓泡通入阴极区，将阴极电极产生的氢气收集并进入缓冲罐5，来自缓冲罐中的氢气通入气体扩散电极进行反应，在温度为25℃下，控制外加负载的阻值为0，此时槽电流密度可达10mA/c m2。控制外加负载的阻值为+∞时，槽电压能达到0.31V，CO2发电设备测得的最大输出功率为3.2W/m2。
实施例3
本实施例的矿化过程如附图1所示。在作为CO2发电设备壳体的容器中，由设置在容器内只允许阳离子透过、而能阻止阴离子透过的阳离子交换膜3，只允许阴离子透过、而能阻止阳离子透过的阴离子交换膜2分隔为阳极区、中间区、阴极区三个区域。在1mol/L的NaCl溶液中加入1mol/L的Na(OH)2形成混合溶液，并加入至阳极区中作为阳极电解液，加入饱和的NaHCO3溶液至阴极区中作为阴极电解液，在中间区加入饱和的NaCl溶液。采用气体扩散电极1作为阳极电极，采用泡沫镍担载Pt/C的电极4作为阴极电极。将CO2气体从作为CO2发电设备壳体的容器底部鼓泡通入阴极区，将阴极电极产生的氢气收集并进入缓冲罐5，来自缓冲罐中的氢气通入气体扩散电极进行反应，在温度为25℃下，控制外加负载的阻值为0， 此时的电流密度能稳定维持在12mA/cm2，在此条件下进行电解反应1h，同时将电解反应1后生成的碳酸氢钠经降温、过滤，并在110℃下烘干后得到的碳酸钠质量为0.210g，对比法拉第电流效率的理论生成0.237g碳酸钠的理论值，生成碳酸钠的转化率高达88.6％，测得的最大输出功率为3.3W/m2。反应完成后，对阳极区的溶液进行酸碱滴定，测试消耗的NaOH量，同时对阴极区产生的碳酸根离子进行化学滴定测试，通过与理论公式的对比，生产碳酸氢钠的电流效率高达93％，同时阳极区酸碱反应的电流效率达到96％。
实施例4
如图2所示，一种CO2矿化燃料电池，包括依次设置的阳极集流层、阳极气室板框、氢气扩散电极、阳极液体室板框、阴离子交换膜、中间室板框、阳离子交换膜、阴极室板框、阴极电极和阴极集流层，阳极集流层和阴极集流层通过电路连接，所述阳极气室板框上设置有原料氢气进出口，所述阴极室板框上设置有载气入口(也可封闭该入口)和产品氢气出口，所述阳极液体室板框、中间室板框和阴极室板框上分别设置有相应电解液的进出口；所述阴极室板框上电解液的入口与阴极缓冲罐相连，所述阴极室板框上电解液的出口也与阴极缓冲罐相连形成循环回路，使反应后的电解液回到阴极缓冲罐中循环使用，同时在阴极缓冲罐上设置CO2气体入口，并在所述阴极缓冲罐中或其出料口处设置固液分离装置；所述中间室板框上的电解液入口与中间缓冲罐相连，通过缓冲罐向中间区供给电解液，所述中间室板框上的电解液出口与中间缓冲罐相连，使反应后的电解液回到中间缓冲罐中循环使用，同时所述中间缓冲罐上设置有钠盐给料口；所述阳极液体室板框上的电解液入口与阳极缓冲罐相连，通过缓冲罐向阳极区供给电解液，所述阳极液体室板框上的电解液出口可与浓缩分离装置相连，三个液体腔室(阳极液体室、中间室和阴极室)中的电解液分别通过蠕动泵的驱动来实现流动或循环。
三个液体腔室的内容积为15ml，阴离子交换膜(AEM)放置在中间室和阳极室之间(面积S＝4cm2)。阴离子交换膜CEM(S＝4cm2)放置在中间室和阴极室之间。阳极电极为气体扩散电极(S＝3.24cm2)，阴极为以Pt/C为催化剂的电极(S＝3.24cm2)。装置的阳极侧接有一个H2钢瓶来向气体扩散电极提供氢源，氢气从阳极的进气口进，出气口出。装置的阴极进气口接有一个N2钢瓶，实验中向载气入口以10ml/min的流量通入N2，将阴极生成的H2从产品氢气出口吹扫出来(吹扫步骤是为了更准确的检测氢气的生产量，实际应用中可省略氮气吹扫和相应的装置)。阴极侧的外部缓冲罐接有一个CO2钢瓶。阴阳两极均使用不锈钢网做集流层。
电极的制备
气体扩散电极实际上有三层结构：集流层、碳布和催化层。具有填平层的碳布上负载 1mg/cm2的Pt催化剂(上海河森电气有限公司)。随后，将碳布与集流层的钛网叠放在一起在5MP、25℃的条件下压制10min，从而制得气体扩散电极。在具有相同表面积的泡沫镍上担载和阳极同样负载量(1mg/cm2)的Pt/C催化剂，在60℃下干燥2h，最后在3MP的压力下压制10min即制得阴极电极。作为可选，所述阴阳极电极均使用喷涂悬浮液的方式负载Pt/C催化剂，所述Pt/C催化剂悬浮液的制备方法如下：首先取0.1g Pt/C(40％Pt)催化剂置于烧杯；随后向其中加入1ml蒸馏水、4ml无水乙醇和4.5g的全氟磺酸溶液，其中乙醇和全氟磺酸分别起分散和粘合的作用；将上述混合物超声后得到黑色的悬浮液即可用于喷涂。
作为可选，制备阴极电极分为以下几个步骤：首先取0.1g Pt/C(40％Pt)催化剂置于烧杯；随后向其中加入1ml蒸馏水、4ml无水乙醇和4.5g的Nafion溶液，其中乙醇和Nafion分别起分散和粘合的作用；将上述混合物超声后得到黑色的悬浮液喷涂到80℃的碳纸上，使碳纸上Pt/C的负载量为1mg/cm2。在60℃下干燥2h，最后在3MP的压力下压制10min即可。
使用时，首先，在每个缓冲罐中加入50ml 1mol/L的NaCl溶液，并用蠕动泵以15ml/min的泵速来抵消离子浓度差异引起的膜电位。反应正式开始前，在系统两极施加5min的3V的电压来彻底消耗掉电极表面附着的O2。这一操作完成后，将100mg Ca(OH)2加到阳极缓冲罐制成溶液(图2部件I)。用质量流量计控制H2气速为10ml/min，通入气体扩散电极进气口(图2部件b)。阴极缓冲罐通入CO2的速率控制在10～20ml/min。整个实验过程中外循环和反应室之间的液体流量控制在15ml/min，以确保整个系统的稳定。在系统的阴极和阳极之间接入电子负载(ItechIT8511)。反应开始后，立刻能够检测到电流的产生，通过调整负载大小可以控制输出电压和输出功率密度的大小。
实验开始后，将100mg分析纯的氢氧化钙加入到CMFC系统的阳极侧，中间室加入饱和的NaCl溶液，阴极侧加入1mol/L的NaCl溶液。随后将纯度为99.99％CO2(20ml/min)通入阴极液，此时立刻有电流产生，并且随着CO2的持续注入系统产生的电压和功率密度达到稳定。体系中阳极的代表反应是Ca(OH)2+H2+2Cl-→CaCl2+2H2O+2e-，阴极通过反应2CO2+2H2O+2e-+2Na+→2NaHCO3+H2生成NaHCO3。
在电流密度2.5A/m2下每隔30分钟定量取样测定阴极侧HCO3 -浓度变化。HCO3 -浓度的线性增加，表明在阴极液中不断生成碳酸氢钠。计算得到生成NaHCO3的平均电流效率(电子进入所述的NaHCO3产物的百分数)为91.4％。运用离子色谱法测定了氯离子在阳极侧的浓度变化，从而测定了在阳极侧产生的CaCl2的量。氯离子含量的线性增长符合预期，在120min内生成CaCl2的平均电流效率经计算为93.4％。
在产电过程中，用气相色谱来测定CMFC系统中阳极气室板框进口气体与出口气体的组成。实验中已经检测到阳极消耗氢气，阴极产生氢气。整个过程中H2的作用在于加快电子的传输速率，因此，反应式1不应该存在H2净的化学计量生成和消耗。通过气相色谱计量生成和消耗的H2所占的比率，我们发现阳极H2消耗的比例与阴极H2生成的比例很接近，这也从实验上证明了两极生成和消耗的量是相等的。
实验中通过酸碱中和滴定的方法测定溶液中NaHCO3的溶度：每隔半小时从阴极取样0.5ml转入锥形瓶，滴加3滴甲基红-溴甲酚绿指示剂并加入适量的蒸馏水，溶液呈亮绿色，然后用浓度0.0011mol/L的HCl滴定上述溶液至暗红色。实验中为了避免Na2CO3的影响，在对照组加入酚酞指示剂。根据反应前后溶液中HCO3 -的浓度差(Δc)和电解液的体积(V)来计算生成的NaHCO3的量m：m＝Δc×V。在阳极侧，通过测定溶液中Cl-的浓度(C1)和Na+的浓度(C2)来计算溶液中CaCl2的浓度：C＝(C1-C2)/2。其中Na+的含量通过原子吸收光谱测定，Cl-的含量通过离子色谱测定。根据实验结果可知，阳极生成CaCl2，阴极生成NaHCO3。在阴极侧，CO2通入溶液后形成H2CO3，生成的H2CO3很快分解为H+和HCO3 -，溶液中H+得到电子从而生成H2，而HCO3 -留在溶液中。在阳极侧，H2失去两个电子变成H+，H+溶解Ca(OH)2生成H2O和Ca2+。在内部电场作用下，中间盐溶液槽向两极提供Na+和Cl-。系统中AEM和CEM通过选择性的使Na+进入阳极、阴离子进入阴极，从而避免了生成的CaCl2与NaHCO3的混合。通过对样品进行XRD和TGA分析发现，产品NaHCO3的纯度达到99.4％。
实施例5
CO2对体系的影响
采用与实施例4相同的设备和操作步骤进行试验。唯一不同的是当产电过程达到稳定的时候，用10ml/min的N2代替CO2通入阴极反应缓冲罐。随后，输出电压和输出功率密度逐渐降低并最终降为0，此时，重新把CO2代替N2通入阴极缓冲罐，系统马上再次产生电压和电流。在整个过程中，每隔60s记录一次输出电压和功率，同时测定记录阴极侧的pH值变化。结果表明，当系统通入CO2后，生成的H2CO3导致阴极pH降低，此时伴随着电能的产生。一旦用N2代替CO2，溶液中的H+将不足以捕捉阳极产生的电子。在这种情况下，H2O将扮演电子的受体，生成H2的同时产生OH-。这将导致pH的升高，产电过程也将逐渐停止。
Ca(OH)2对体系的影响
采用与实施例4相同的设备和操作步骤进行试验。唯一不同的是在反应的初始阶段在阳极加入1ml饱和的Ca(OH)2溶液。随着产电过程的进行，阳极的Ca(OH)2逐渐被消耗，输出 电压和功率密度逐渐降低并最终变为0。随后，再次向阳极加入1ml饱和的Ca(OH)2溶液，系统再次对外输出电能。
向阳极加入1ml的饱和Ca(OH)2溶液，阳极pH立刻升高并产生电能。随着反应的进行，溶液中的Ca(OH)2逐渐被消耗，pH降低并且输出能量减少为零。当新的1ml的饱和Ca(OH)2溶液加入后，溶液的pH升高并再次对外输出能量。
根据上述实验结果，我们可以得出结论：CO2和CaCl2在体系中起的作用是在阴阳两极构建一个pH差。当阳极有H2通入的时候，这个pH差就会转化为氧化反应对H+/H2在两极的电位差，当外部导通的时候，体系就会向外输出电流。在这个过程中，CO2向阴极提供H+，Ca(OH)2向阳极提供OH-，根据能斯特方程，理论电池电压可以按照方程(式2)计算：
Ecell＝0.0591(pHanode-pHcathode)   (式2)
为了更进一步地证实这个理论，我们绘制了电池电压和两极pH差之间的关系曲线，结果显示，增大两极的pH差将增大开路电压，这和方程(式2)结果是一致的。
在产电过程中，阴极槽生成的NaHCO3的水解将影响溶液的pH。为了测试这种影响，实验中在阴极加入不同的电解质(以NaCl代替NaHCO3)。结果显示，CMFC体系下1mol/L的NaCl的产电效果要好于饱和的NaHCO3溶液。这是因为前者在体系下产生的pH差大于后者，从而导致了前者有更高的输出电压和能量。实验中达到的最大输出能量为5.5W/m2，最大开路电压OCV为0.452V。
实施例6
采用实施例4所述的装置，实验中阳极加入Ca(OH)2，中间极加入饱和的NaCl溶液，阴极加入饱和的NaHCO3溶液，反应开始阶段先不通入CO2，阴极没有了CO2的通入，在能量密度为30.86A/m2的条件下，溶液中残存的HCO3 -会为反应提供H+并变成CO3 2-。但是随着反应的进行，输出能量密度会逐渐由3.55W/m2降到2.96W/m2；此时，向阴极缓冲罐中通入过量的CO2，这个过程中，CO3 2-将转化为HCO3 -，当碳酸氢钠在溶液中的溶解度达到最大值后将析出晶体，经过固液分离，固相可用于制备碳酸氢钠或碳酸钠，液相返回CMFC电池系统，输出能量立刻回升至3.55W/m2，如此循环，可持续产出电能和碳酸氢钠或碳酸钠。
实施例7 其他碱性原料的矿化产电性能
概念验证阶段，我们在试验中利用的是分析纯的Ca(OH)2。为了检验这个系统能否有效的利用含有Ca(OH)2的工业固废，实验中将从化工厂得到的电石渣和水泥窑灰作为碱源加入阳极区。实验中，阳极区和阴极区各加入50ml 1mol/L的NaCl溶液，中间室加入50ml的饱 和NaCl溶液。在产电操作中，按间隔1mA的梯度将电流值从0调到25mA，并在每个电流值下保持120min。整个过程中，体系的温度维持在25℃。结果表明，两种废渣都能用于产电，其中电石渣的反应活性与分析纯的Ca(OH)2非常接近。
在采用不同的胺类作为碱源的实验中按照上面描述的相同流程进行相关实验。结果表明：10％的氨水、MEA和TEA三种不同种类的胺在相同的反应条件下能产出的功率密度分别为3.71、2.81和1.02W/m2。
实施例8 CMFC体系的稳定性
研究中考察了CMFC体系的稳定性。具体实验时在系统的阴极和阳极各加入300ml1mol/L的NaCl溶液，中间室加入300ml饱和的NaCl溶液。实验开始后在阳极添加适量的电石渣，并将一定流量的CO2通入阴极电解液。固定电流密度为30.86A/m2，系统连续运行17h以上，在此期间，每隔2min测定一次输出功率。结果显示，系统具有良好的稳定性。
实施例9 CO2浓度对产电效果的影响
火电厂排放的烟道气中CO2的浓度一般较低(通常<20％)，为了研究CMFC系统直接处理工业烟道气的可能性，采用混合的N2/CO2来考察CO2浓度对产电过程的影响。在阳极区和阴极区各加入50ml 1mol/L的NaCl溶液，中间室加入50ml饱和的NaCl溶液，实验中向阴极电解质通入不同浓度(10％、20％、50％、100％)的CO2混合气体，气速为100ml/min。其中CO2的浓度通过调整N2和CO2的流速来控制。相关的产电过程所用设备和操作方法参见实施例4。实验结果表明CO2含量低至10％时，仍然可以产电。CO2浓度越高，输出的功率密度越高。这是由于不同浓度的CO2导致阴极侧具有不同的pH值。
以上所述仅为本发明的优选实施例，对本发明而言仅是说明性的，而非限制性的；本领域普通技术人员理解，在本发明权利要求所限定的精神和范围内可对其进行许多改变，修改，甚至等效变更，但都将落入本发明的保护范围。

Claims (16)

  1. 一种矿化CO2制取碳酸氢钠或碳酸钠对外输出电能的方法，其特征在于，基于CO2矿化利用原理，结合膜电解技术，利用CO2所具有的酸性和反应溶液的碱性促使反应自发进行的同时实现产物的分离，在制取碳酸氢钠或碳酸钠的同时将反应释放的能量通过膜电解装置转换为电能输出。
  2. 根据权利要求1所述的方法，其特征在于，将阴离子交换膜和阳离子交换膜置于容器中，将容器分隔为阳极区、中间区和阴极区三个部分，在阳极区的液体中加入碱性物料构成阳极电解液，在中间区液体中加入作为电解反应原料的钠盐构成中间电解液，在阴极区加入阴极电解液，连接阴阳电极形成电流通路，中间电解液中的钠盐分解形成的阴离子和钠离子在电流作用下分别通过阴离子交换膜和阳离子交换膜进入到阳极区和阴极区，在阳极区，氢气在阳极电极上氧化生成的氢离子与加入的碱性物料发生中和反应使透过阴离子交换膜的阴离子与阳极电解液中的阳离子结合生成盐；在阴极区，向阴极电解液中持续通入CO2气体，阴极电解液中的氢离子在阴极电极上还原为氢气，使得阴极电解液中的CO2转化为碳酸氢根，与钠离子生成碳酸氢钠，利用阴阳极区之间pH值之差形成的电势，在反应进行时，阳极区发生的酸碱中和反应和阴极区发生的CO2矿化反应所释放的能量以H2作为媒介转变为的电能实现对外产电。
  3. 根据权利要求2所述的方法，其特征在于，反应完成后将阴极区产生的碳酸氢钠移出经过滤得到固体碳酸氢钠，或进一步烘干得到固体碳酸钠。
  4. 根据权利要求2所述的方法，其特征在于，所述钠盐选自氯化钠、硫酸钠和硝酸钠。
  5. 根据权利要求2所述的方法，其特征在于，所述阳极电解液和\或阴极电解液中含有钠盐。
  6. 根据权利要求2所述的方法，其特征在于，所述阳极区加入的碱性物料为工业生产过程中所产生的含有氢氧化钙、氢氧化钠、氨水、氢氧化钾中的至少一种碱性物料。
  7. 根据权利要求2所述的方法，其特征在于，所述用于将氢气氧化为氢离子的阳极电极为气体扩散电极。
  8. 根据权利要求2所述的方法，其特征在于，所述阴极电极为在泡沫镍上担载Pt/C催化剂制成的，其中Pt担载量一般在0.1-0.5mg/cm2范围。
  9. 根据权利要求2所述的方法，其特征在于，将阴极区产生的氢气作为原料氢气加入阳极区。
  10. 根据权利要求2所述的方法，其特征在于，及时将阴阳极反应产生的产物采出。
  11. 一种矿化CO2制取碳酸氢钠或碳酸钠对外输出电能的设备，其特征在于，包括阳极区、中间区、阴极区，阳极区与中间区之间通过阴离子交换膜隔开，中间区与阴极区之间通 过阳离子交换膜隔开，所述阳极区、中间区、阴极区能够容纳对应的电解液，所述阳极区设置有阳极电极,所述阴极区设置有阴极电极，阴、阳电极通过电路连接，阳极区设置有原料氢气入口，阴极区设置有CO2气体入口和产品氢气出口。
  12. 根据权利要求11所述的设备，其特征在于，所述阴极区与结晶器、固液分离装置连接。
  13. 根据权利要求11所述的设备，其特征在于，阴极区的电解液的入口与阴极缓冲罐相连，通过缓冲罐向阴极区供给电解液，所述阴极区的电解液的出口与阴极缓冲罐相连，使反应后的电解液回到阴极缓冲罐中循环使用，同时将所述阴极区的CO2气体入口设置在阴极缓冲罐上，并在所述阴极缓冲罐中或其出料口处设置结晶和固液分离装置。
  14. 根据权利要求11所述的设备，其特征在于，各腔室中电解液的流动管道或循环管道上设置有流体输送泵。
  15. 根据权利要求11所述的设备，其特征在于，所述设备包括依次设置的阳极集流层、阳极气室板框、氢气扩散电极、阳极液体室板框、阴离子交换膜、中间室板框、阳离子交换膜、阴极室板框、阴极电极和阴极集流层，阳极集流层和阴极集流层通过电路连接，所述阳极气室板框上设置有原料氢气进出口，所述阴极室板框上设置有CO2气体入口和产品氢气出口，所述阳极液体室板框、中间室板框和阴极室板框上分别设置有相应电解液的进出口。
  16. 根据权利要求15所述的设备，其特征在于，所述阴极室板框上电解液的入口与阴极缓冲罐相连，所述阴极室板框上电解液的出口也与阴极缓冲罐相连形成循环回路，使反应后的电解液回到阴极缓冲罐中循环使用，同时在阴极缓冲罐上设置CO2气体入口，并在所述阴极缓冲罐中或其出料口处设置结晶和固液分离装置。
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