CN107437629A - Make the CO of basic nature agent with sodium acid carbonate2Mineralising electricity-generating method - Google Patents

Make the CO of basic nature agent with sodium acid carbonate2Mineralising electricity-generating method Download PDF

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CN107437629A
CN107437629A CN201710637992.2A CN201710637992A CN107437629A CN 107437629 A CN107437629 A CN 107437629A CN 201710637992 A CN201710637992 A CN 201710637992A CN 107437629 A CN107437629 A CN 107437629A
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mineralising
electricity
sodium acid
acid carbonate
anode
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CN107437629B (en
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谢和平
王昱飞
刘涛
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Sichuan University
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Sichuan University
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    • 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
    • H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • 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
    • 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
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
    • H01M8/0631—Reactor construction specially adapted for combination reactor/fuel cell
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The present invention discloses the CO that a kind of sodium acid carbonate makees basic nature agent2Battery is divided into anode region and cathodic region by mineralising electricity-generating method, cation-exchange membrane, and cathodic region contains supporting electrolyte, the leaching liquid that anode region is formed containing alkaline solid waste and sodium acid carbonate, after anode and cathode forms path, CO2It is passed through negative electrode and ionizes out H+And HCO3 ‑, H+It is H in cathodic reduction2And it is H to be recycled back to anodic oxidation+, then the OH with anolyte‑Neutralize, HCO3 ‑With the Na from anode region+Generate sodium acid carbonate.Sodium acid carbonate is continuously generated and is recycled to anode region in catholyte leaches solid caustic soda, filtering leaching suspension again, and filtrate continues to serve as anolyte；OH will be consumed simultaneously‑Anolyte be recycled to cathodic region.This method can lift battery electricity generation performance by heating, be generated electricity suitable for alkalescent solid waste.Three emission reduction, fixed-end forces and generating purposes can be realized simultaneously applied to steel-making industry, there is higher practical value.

Description

Make the CO of basic nature agent with sodium acid carbonate2Mineralising electricity-generating method
Technical field
The invention belongs to electrochemical field, and in particular to one kind promotes low alkalinity using sodium acid carbonate as basic nature agent Industrial Solid basic hydrolysis is simultaneously changed into high-concentration alkali liquor, so as to strengthen CO2The method of mineralising battery electricity generation performance.
Background technology
CO in air2Concentration rises, how emission reduction CO2, to cooling earth into For global sciences problems.At present, by CO2It is a kind of CO as discarded object seal up for safekeeping2Emission reduction approach, such as geological storage and Seal up for safekeeping ocean.And by CO2As chemical raw material generative fuel or to be converted into industrial chemical be then another selection.However, Existing CO2Discharge-reducing method still faces cost height, the technical barrier of high energy consumption, reduces CO2Emission reduction energy consumption, realize that economy carbon subtracts Row is global scientific circles, the common objective of industrial quarters.Analyzed from thermodynamics, CO caused by fossil fuel2It is not nature The carbon compound of minimum energy in boundary.Substantial amounts of solid carbonate in nature be present, these solid carbonates can be in nature Even years up to a million in years up to ten thousand are stabilized in boundary.Therefore, by CO2It is thermodynamically the change uniquely known to carry out mineralising processing The CO that degree reduces2Utilization ways.
In research before, inventor developed mineralising CO2Preparing sodium bicarbonate or sodium carbonate externally export electric energy Method (patent CN201410319920.X), realize CO first2Chemical energy in mineralization process is converted directly into electric energy, Worldwide take the lead in proposing and realizing a kind of CO for exporting energy2Emission reduction new way is simultaneously developed with independent intellectual production The first generation CO of power2Mineralising battery.This method uses industrial alkaline waste and sodium chloride as raw material, by CO2Mineralization process is released The chemical energy put is converted into electric energy, while the sodium acid carbonate of output high added value.The peak power output density of this method is 5.5W/m2, maximum open circuit voltage 0.452V.
In order to improve CO2The performance of mineralising battery simultaneously optimizes CO2The internal structure of mineralising battery, inventors also developed Strengthen CO by the use of saltcake as reaction medium2The method of mineralising battery electricity generation performance, can using the sulfate radical in saltcake solution Reacted with calcium ion and generate calcium sulfate precipitation, so as to promote the water of calcium hydroxide in the alkaline solution of Industrial Solid Waste formation Solution, the pH value of solution is improved, promote CO2Mineralising efficiency of fuel cell generation.Meanwhile to reduce ion diffusional resistance as breach, design is simultaneously The CO of a new generation is manufactured2Mineralising battery.Research shows, in second generation CO2Using saltcake as reaction medium in mineralising battery Afterwards, the open-circuit voltage of battery is improved to 0.552V, and maximum power density is improved to 34.5W/m2, respectively than using sodium chloride and electricity Rock ballast improves 10.4% and 55.4%.
In theory, CO2Mineralising generation technology is raw materials used to can be generalized to all Alkaline minerals, including industrial alkaline is consolidated Useless (slag, cement dust, carbide slag, flyash etc.), alkaline waste water (dyeing waste water, paper-making industrial waste water etc.) are naturally alkaline Mineral (wollastonite, olivine, shepardite etc.) can be used as CO2Mineralising generating raw material.However, sent out according to the research of the present inventor Existing, in numerous industrial alkaline solid wastes, only carbide slag can apply to the first generation and second generation CO2Mineralising battery.Galvanic anode OH in liquid-Can constantly it be consumed in electrode surface, thus OH is leached in CaO content and basic nature agent in industrial alkaline solid waste-Energy Power is that an important factor for whether mineralising battery is feasible influenceed.Dissociate CaO content ＞ 70% in carbide slag, other industrial alkaline solid wastes CaO content be far below this, thus be difficult to be applied to existing CO2Mineralising generating system.If it is desired that CO2Mineralising battery turns into one The extensive processing CO of kind2, just must be to preceding two generation CO with the technology of solid waste2Mineralising battery is improved, and is applied to it more Low alkalinity solid waste.
By taking slag as an example, steel-making industry is per the substantial amounts of CO of annual meeting output2(the 6-7% of whole world total carbon emissions amount；0.28-1 Ton CO21 ton of steel of/production) and slag (global hundred million tons/year of 3.15-4.2), estimated according to alkali number, it is potential to generate electricity 5,000,000,000 degree.But The content of free CaO seldom (0%-10%), is difficult with free CaO in slag and hydrolyzes solution of the generation compared with strong basicity in slag Applied to the existing first generation and second generation CO2In mineralising generation technology.However, if CO can be carried out as raw material using slag2Ore deposit Elelctrochemical power generation has the advantage that：1st, collaboration utilizes slag and CO2It is carried out in situ CO2Mineralising, which generates electricity, will substantially reduce mineralising raw material fortune It is defeated to arrive CO2Cost of transportation near emission point, there is potential inexpensive advantage；2nd, the carbonating of slag can improve its machinery Performance, it is set to be more suitable as construction material, by CO2Slag after mineralising processing has industrial utility value；3rd, produce The electric energy gone out can supplement as the energy of steelmaking process.Therefore, CO is carried out using slag2Mineralising, which generates electricity, has emission reduction CO2, obtain Power taking energy, the triple role for handling Industrial Solid Waste, it is clear that be one and be expected solve the energy and environment contradiction, it is ensured that sustainable development Great potential approach.
Therefore, the alkalescence fully in extraction industrial alkaline solid waste, develop and consolidate suitable for the alkalescence such as slag is relatively low The novel C O of alkali raw material2Mineralising battery system, further improves electricity generation performance, can make CO2Mineralising battery has stronger reality should With value.
The content of the invention
For existing CO2Mineralising cell power generation technology is not applied for the problem of Industrial Solid Waste raw material of low alkalinity, this hair Bright purpose is to provide a kind of new CO2Mineralising electricity-generating method, slag is fully extracted by the use of sodium acid carbonate as basic nature agent Deng the alkalescence in the relatively low solid waste of alkalescence, CO is widened2The application field of mineralising generation technology, and further improve CO2Mineralising The electricity generation performance and open-circuit voltage of battery.
The third generation CO that the present invention is formed2Mineralising cell power generation technology is based on brand-new chemical reaction process (reaction 1)：
CO2+Ca(OH)2=CaCO3+H2O Δs G=-72.62KJ/mol (1)
Specifically, in the CO2The chemical reaction that mineralising inside battery mainly occurs is as follows：
Cathodic region：2CO2+2H2O+2e-+2Na+→2NaHCO3+H2 (3)
Anode region：2Ca(OH)2+H2+2HCO3 -→2CaCO3+4H2O+e- (4)
Present invention sodium acid carbonate makees the CO of basic nature agent2Mineralising electricity-generating method, mainly includes：By cation-exchange membrane It is placed in CO2In mineralising battery case, anode region and cathodic region are divided the container into, is added when starting reaction, in cathodic region and supports electricity Liquid is solved, anode region adds alkaline solid waste and the leaching liquid containing NaOH generated after reaction of sodium bicarbonate, and connection anodic-cathodic is formed Current path, by CO2H is ionized out after being passed through cathodic region+And HCO3 -, the H that ionizes out+H is reduced on negative electrode2, remaining HCO3 - The Na of coming is passed through with from anode region+With reference to generation NaHCO3, the H of negative electrode generation2It is recycled back to anode and in the presence of anode electrode Release electronics is oxidized to H+, H+With OH in anolyte-Generation neutralization reaction.
CaO in alkaline solid waste is hydrolyzed to Ca (OH)2NaOH and CaCO is generated with reaction of sodium bicarbonate3。
In above-mentioned CO2In mineralising electricity-generating method, while the NaOH in anolyte is constantly consumed, in catholyte NaHCO3It is continuously generated, as the NaHCO in catholyte3Rise to more than or equal to after 1mol/L, be recycled to anode region again with work Industry solid caustic soda carries out leaching reaction, therefore, NaHCO3In the CO2Recycled in mineralising power generation process；Then anode region is hanged Supernatant liquid is filtered, and filtrate continues to serve as anolyte, after filter residue drying, construction material can be used as standby；Simultaneously will consumption OH-Anolyte be recycled to cathodic region as catholyte.
In cathodic region, CO2With H2Ionization generates H after O reactions+, in anode region, NaHCO3Alkaline solid waste is promoted to ionize out OH-.Therefore pH difference is established between cathode and anode, in H+/H2Under the assistance of oxidation-reduction pair, this pH difference Change the electrical potential difference between yin, yang electrode, turn on CO2Negative and positive the two poles of the earth of mineralising battery just can realize the output of electric current.
Using NaHCO3CO as basic nature agent2In mineralising electricity-generating method, NaHCO3In HCO3 -Energy and Ca2+Knot Symphysis is into CaCO3Precipitation, promote the free CaO in Industrial Solid Waste to hydrolyze and be changed into the alkali lye (reaction 2) of high concentration, significantly carry High CO2CO is expanded while mineralising generating efficiency2The scope of application of the mineralising battery to solid caustic soda.
NaHCO3Effect：NaHCO3+Ca(OH)2→NaOH+CaCO3+H2O (2)
In the above-mentioned technical proposal of the present invention, described alkaline solid waste can be carbide slag in industrial processes, At least one of cement dust, incineration firing discarded object, slag, flyash.
When described alkaline solid waste is that CaO content is less than 50%, or less than 30%, even below 20% industrial alkaline During solid waste, CO of the invention2Mineralising electricity-generating method and preceding two generation CO2Mineralising generation technology is compared, and embodies astonishing effect Fruit.Because preceding two generation CO2Mineralising generation technology can only use the carbide slag that CaO content is higher than 70%, and the method for the present invention can So that the industrial alkaline solid waste of above-mentioned CaO content is included into application.It is of the invention as a more amazing result CO2CaO content can be less than 10% alkaline solid waste by mineralising electricity-generating method, be to be only by CaO content more precisely 1.06% slag is as raw material producing electricity.Although, will because the difference of solubility according to known to the knowledge of those skilled in the art Ca2+It is combined into CaCO3Than being combined into CaSO4It is more beneficial for Ca (OH)2Ionize out OH-, but the CO of the present invention2Mineralising generating side The so low solid waste of CaO content can be used to generate electricity by method unexpectedly, and use Na2SO4When, CO2Mineralising battery is using slag as raw material It can not carry out at all, expection of such effect well beyond those skilled in the art.
In the above-mentioned technical proposal of the present invention, the CO2The reaction temperature of mineralising battery is normally controlled in 10-100 DEG C In the range of.As another amazing result of the invention, inventor has found, is using sodium acid carbonate as basic nature agent When, CO of the invention2From when rising to 35~45 DEG C for 25 DEG C, maximum power density significantly raises mineralising cell reaction temperature.According to The specific embodiment of the present invention, when rising to 40 DEG C from 25 DEG C, maximum power density is by 64.55W/m2Rise to 76.33W/m2, lifting amplitude is up to 18.25%.With this formation sharp contrast, when being leaching agent with sodium sulphate, temperature On power density almost without influence.According to the analysis of inventor, this may raise the mistake for reducing evolving hydrogen reaction of the present invention with temperature Current potential, while the reaction rate for accelerating electrode is relevant.Therefore, CO of the present invention2Mineralising electricity-generating method, preferably its reaction Temperature be 35~45 DEG C, more preferably 40 DEG C, to lift the electricity generation performance of mineralising battery.
In the above-mentioned technical proposal of the present invention, when starting reaction, the purpose that supporting electrolyte is added in cathodic region is Strengthen solution conductivity performance, the supporting electrolyte can be NaCl, NaHCO3、NaNO3、Na2SO4In one of which, preferentially From the NaCl solution that concentration is 0.5-5mol/L.
In the above-mentioned technical proposal of the present invention, described cathode electrode is made of metal platinum, Metal Palladium or metallic nickel Porous electrode.
In the above-mentioned technical proposal of the present invention, the anode electrode is gas-diffusion electrode.Anode electrode utilizes negative electrode Hydrogen source of the hydrogen caused by electrode as anode gas diffusion electrode.Hydrogen caused by cathode electrode can specifically be passed through Hydrogen gas buffer enters anode electrode.
In the above-mentioned technical proposal of the present invention, anode region, the solution in cathodic region can be selected using corresponding molten Liquid storage tank stores, and solution is circulated between anode region, cathodic region and corresponding storage tank by circulating pump.
In the above-mentioned technical proposal of the present invention, CO is passed through2Mode can use independent carbon dioxide absorption tower, also may be used By bubbling by CO2It is passed through in solution, those skilled in the art can be according to actual current size to being passed through CO2Amount adjusted Control.It is above-mentioned to be passed through CO2Carry out at ambient pressure, but appropriate increase air pressure contributes to the quick generation of reaction, and the present invention provides excellent It is 0.1-0.2Mpa to select pressure limit.
The present invention uses NaHCO3CO as basic nature agent2Mineralising electricity-generating method, compared with the conventional method, have such as Lower advantage：
1st, the pH differences for maintaining cathode and anode are to ensure CO2The premise that mineralising generating can be carried out, bigger pH differences can produce Raw higher open-circuit voltage, NaHCO3Energy and Ca2+Reaction generation CaCO3Precipitation, the hydrolysis of the free CaO in solid caustic soda is promoted to be changed into The alkali lye of high concentration, so as to improve CO2The electricity generation performance of mineralising battery, when catholyte is to be saturated H2CO3NaCl solution When, anode region uses 1mol/L Na2SO4Open-circuit voltage be 0.55V, maximum power density 34.5W/m2, and work as anode region Using 1mol/L NaHCO3Afterwards, open-circuit voltage is increased to 0.59V, maximum power density 64.55W/m2, open-circuit voltage and maximum 9.3% and 88.0% has been respectively increased in power density；
2nd, the present invention reduces the overpotential of electrode reaction by the way of temperature is raised, and accelerates the reaction speed of electrochemistry Rate, further improve CO2The electricity generation performance of mineralising battery, for example, with NaHCO3As leaching agent maximum electricity production power density by 64.55W/m at 25 DEG C276.33W/m when being promoted to 40 DEG C2, lifting amplitude is up to 18.25%；
3、NaHCO3The alkalescence in solid caustic soda can be extracted to a greater extent, for the relatively low industrial alkaline solid waste of CaO content, used Na2SO4Make the CO of leaching agent2Mineralising battery can not be applied, but the mineralising battery of the present invention still can be used as original Material, it might even be possible to solid waste raw material range is extended to containing free CaO be only 1.06% slag；
4th, using NaHCO3As weak base leaching agent, CO will be made2Mineralising generation technology can with make steel industry fixed-end forces, CO2Emission reduction is combined, and realizes CO2In the direct mineralising in industrialized regions close to emission point, substantially reduce mineralising raw material and transport CO2 Cost of transportation near emission point, while carbonating processing has been carried out to slag, its mechanical performance is significantly strengthened, be more suitable for As construction material, therefore realize steel mill " slag processing-emission reduction CO2The integrated technique of-comprehensive utilization of waste materials ", it is one What is be expected solves the energy and the sustainable approach to development of environment contradiction.
Brief description of the drawings
Fig. 1 uses NaHCO for the present invention3CO as basic nature agent2The course of reaction schematic diagram of mineralising electricity-generating method； Wherein, 1- gas-diffusion electrodes (anode)；2- cation-exchange membranes；3- cathode for hydrogen evolution；4- hydrogen gas buffers；
Fig. 2 is NaHCO in embodiment 13The XRD of filter residue before and after leaching；
Fig. 3 is NaHCO in embodiment 13The TGA figures of filter residue after leaching；
Fig. 4 is the carbide slag of embodiment 1 and Na2SO4Influence figure of the solid-to-liquid ratio of solution to carbide slag conversion ratio；
Fig. 5 is the I-V characteristic curve of cell figure that embodiment 2 measures at 25 DEG C and 40 DEG C；
Fig. 6 is the I-V characteristic curve of cell figure that comparative example 1 measures at 25 DEG C and 40 DEG C；
Fig. 7 is by the CO of the present invention2Mineralising electricity-generating method is applied to the fixed-end forces and CO of steel-making industry2The one of emission reduction Change technical though schematic diagram.
Embodiment
Below in conjunction with the accompanying drawings, by embodiment, the present invention is described in further detail.It is important to point out that below Embodiment is served only for that the present invention is described further, it is impossible to is interpreted as limiting the scope of the invention, art Personnel be skillful at according to foregoing invention content, some nonessential modifications and adaptations are made to the present invention and are embodied, It is easily able to very much, therefore, such improvement should still fall within protection scope of the present invention with adjustment.
Embodiment 1
The present embodiment uses NaHCO3CO as basic nature agent2The chemical reaction process reference chart of mineralising electricity-generating method 1.As CO2In the vessel shell of mineralising battery, the cation of anion-permeable can be prevented by only allowing cation permeable Exchange membrane 2 is divided into anode region and cathodic region Liang Ge regions.Meanwhile anode electrode is used as using hydrogen diffusion electrode 1, using carbon The electrode 3 that cloth supports Pt/C is used as cathode electrode.Prepare 100ml 1mol/L NaCl and 1mol/L NaHCO3Mixing it is molten Liquid, then progressively add 2g carbide slags into solution and form suspension, and under 300rpm rotating speed after stirring 20min, will be outstanding Supernatant liquid is filtered, and filtrate is circulated with 20ml/min speed between storage tank and anode region, after filter residue is dried at 60 DEG C, profit With XRD and thermobalance analysis filter residue change of component and salinity, XRD as shown in Fig. 2 TGA as shown in figure 3, result table Free CaO in bright carbide slag has been completely reformed into CaCO3。
100ml saturated sodium bicarbonate solution is equally pumped into CO with 20ml/min rate loop2The negative electrode of mineralising battery Area, while CO2Cathodic region is blasted with 20ml/min speed.A power source loads (Itech is connected between a cathode and an anode IT8511), power output is by controlling the resistance value of power source loads to be adjusted.In the case where temperature is 25 DEG C, electric current is set from 0mA Maximum output current is risen to 2mA/s speed, the I-V characteristic curve of cell now measured shows CO2Mineralising battery is opened Road voltage is 0.59V, maximum power density 64.55W/m2, and first generation CO2The open-circuit voltage of mineralising battery is 0.452V, most High power density is 5.5W/m2, second generation CO2The open-circuit voltage of mineralising battery is 0.55V, maximum power density 34.5W/m2。
By 1mol/L NaHCO3With 1mol/L Na2SO4Replacement is used as leaching liquid, when carbide slag content is 2g/ in solution During L, the conversion ratio of carbide slag is also only 85.9%, pH value 12.64；And when carbide slag content reaches 10g/L, carbide slag turns Rate further drops to 56.5%, and pH value is only capable of further up to 13.15.Fig. 4 illustrates carbide slag and Na2SO4Solution Influence of the solid-to-liquid ratio to carbide slag conversion ratio.
It can be seen that use NaHCO3More abundant as extraction of the basic nature agent to carbide slag alkalescence, CaO conversion ratio reaches To 100%, and improve CO2The electricity generation performance of mineralising battery, hence it is evident that better than Na2SO4。
Embodiment 2
The present embodiment uses NaHCO3CO as basic nature agent2The chemical reaction process reference chart of mineralising electricity-generating method 1.As CO2In the vessel shell of mineralising battery, the cation of anion-permeable can be prevented by only allowing cation permeable Exchange membrane 2 is divided into anode region and cathodic region Liang Ge regions.Meanwhile anode electrode is used as using hydrogen diffusion electrode 1, using carbon The electrode 3 that cloth supports Pt/C is used as cathode electrode.Prepare 100mL 1mol/L NaCl+1mol/L NaHCO3Mixed solution, Then 5g carbide slags progressively are added into solution and forms suspension, and under 200rpm rotating speed after stirring 50min, by suspension Filtered, filtrate is circulated with 20ml/min speed between storage tank and anode region, after filter residue is dried at 80 DEG C, utilizes The change of component and salinity of XRD and thermobalance analysis filter residue show that the free CaO in carbide slag is completely reformed into CaCO3.80ml saturated sodium bicarbonate solution is equally pumped into CO with 20ml/min rate loop2The cathodic region of mineralising battery, together When CO2Cathodic region is blasted with 20ml/min speed.A power source loads (Itech is connected between a cathode and an anode IT8511), power output is by controlling the resistance value of power source loads to be adjusted.
It is respectively at 25 DEG C and 40 DEG C in cell reaction temperature, sets electric current to rise to maximum from 0mA with 2mA/s speed Output current, as described in Figure 5, wherein 5 be voltage curve, 6 be power density curve to the I-V characteristic curve of cell now measured. As a result the front and rear CO that heats up is shown2The open-circuit voltage of mineralising battery is stable in 0.59V, and maximum power density from normal temperature when 64.55W/m2Further it is promoted to 76.33W/m2.As temperature rises to 40 DEG C, with NaHCO3CO as basic nature agent2Ore deposit The electricity generation performance of electrochemical cell gets a promotion.
Comparative example 1
Using method similar to Example 2, Na is used2SO4Instead of NaHCO3As basic nature agent, in cell reaction temperature Degree is respectively at 25 DEG C and 40 DEG C, sets electric current to rise to maximum output current from 0mA with 2mA/s speed, now measures As described in Figure 6, wherein 5 be voltage curve, 6 be power density curve to I-V characteristic curve of cell.As a result the front and rear CO that heats up is shown2 The open-circuit voltage of mineralising battery is reduced to 0.52V from 0.55V, and maximum power density is respectively 34.49W/m2And 34.67W/m2。 It can be seen that with Na2SO4CO as basic nature agent2Mineralising battery, electricity generation performance are affected by temperature less.
Embodiment 3
The present embodiment uses NaHCO3CO as basic nature agent2The chemical reaction process of mineralising electricity-generating method is referring to figure 1.As CO2In the vessel shell of mineralising battery, the cation of anion-permeable can be prevented by only allowing cation permeable Exchange membrane 2 is divided into anode region and cathodic region Liang Ge regions.Meanwhile anode electrode is used as using hydrogen diffusion electrode 1, using carbon The electrode 3 that cloth supports Pt/C is used as cathode electrode.Use free CaO content be only 1.06% slag for raw material, by 200g steel Slag adds 100ml 0.2mol/L NaHCO3After solution, 20min is stirred under 300rpm rotating speed, suspension was carried out Filter, the filtrate of leaching are circulated for electricity generation performance and the survey continuously produced electricity with 20ml/min speed between storage tank and anode region Examination.Cathodic region adds the sodium bicarbonate solution that 80ml concentration is 1mol/L, is equally pumped into CO with 20ml/min rate loop2Ore deposit The cathodic region of electrochemical cell, while CO2Cathodic region is blasted with 20ml/min speed.After electrolyte is continually fed into battery, by CO2 Yin, yang the two poles of the earth of mineralising battery are connected (Itech, IT8511) with electronic load, and control electronic load makes electric current be maintained at 10mA, The power output of measure and record battery, until no longer externally electricity production.Test result indicates that using NaHCO3As leaching agent, So that the slag that 200g free CaOs are only 1.06% also can mineralising generating 5.66J.
Comparative example 2
Using method similar to Example 3, Na is used2SO4Instead of NaHCO3It is same using free as basic nature agent The slag that CaO content is only 1.06% is raw material, and control electronic load makes electric current be maintained at 10mA, determines and record the defeated of battery Go out power.As a result show, the 10mA of setting can reached in a flash and within several seconds by reacting the electric current of initial electronic load 0 is rapidly reduced to, excludes to react the influence of initial Unsteady State Response, it is believed that using Na2SO4As basic nature agent simultaneously The alkalescence that can not effectively extract in the solid waste of extremely low free CaO content generates electricity for CO2 mineralisings.
According to above-mentioned it is recognized that while using NaHCO3And Na2SO4Make leaching agent, its anion can be in anode region and industrial soda Property solid waste reaction, by Ca2+Sunk to the bottom with reference to generation, promote OH-Formation, for carbide slag be raw material CO2Mineralising battery is carried out Generate electricity, but for the relatively low solid waste of CaO content, such as slag, Na2SO4It is that can not realize CO as leaching agent2What mineralising generated electricity, And present invention NaHCO3The method for making basic nature agent then obtains unexpected effect.
Based on the achievement in research of the present invention, the method for the present invention can be applied to fixed-end forces, the CO for making steel industry2Subtract In row, gather materials on the spot, treatment in situ, realize steel mill as shown in Figure 7 " slag processing-emission reduction CO2- comprehensive utilization of waste materials " Integrated technique.
Presently preferred embodiments of the present invention is the foregoing is only, is merely illustrative for the purpose of the present invention, rather than to this hair Bright scope is defined.On the premise of design spirit of the present invention is not departed from, those of ordinary skill in the art are to the present invention's The various modifications and improvement that technical scheme is made, it all should fall into the protection domain of claims of the present invention determination.

Claims (10)

1. a kind of sodium acid carbonate makees the CO of basic nature agent2Mineralising electricity-generating method, it is characterised in that put cation-exchange membrane In CO2In mineralising battery case, anode region and cathodic region are divided the container into, is added when starting reaction, in cathodic region and supports electrolysis Liquid, anode region add alkaline solid waste and the leaching liquid containing NaOH generated after reaction of sodium bicarbonate, and connection anodic-cathodic forms electricity Logical circulation road, by CO2H is ionized out after being passed through cathodic region+And HCO3 -, the H that ionizes out+H is reduced on negative electrode2, remaining HCO3 -With From anode region through the Na come+With reference to generation NaHCO3, the H of negative electrode generation2It is recycled back to anode and is released in the presence of anode electrode Electric discharge is oxidized to H+, H+With OH in anolyte-Generation neutralization reaction.
2. sodium acid carbonate according to claim 1 makees the CO of basic nature agent2Mineralising electricity-generating method, it is characterised in that sun While NaOH in the liquid of pole is constantly consumed, the NaHCO in catholyte3It is continuously generated, as the NaHCO in catholyte3Rise to big After equal to 1mol/L, it is recycled to anode region and carries out leaching reaction with alkaline solid waste again, then by anode region suspension Filtered, filtrate continues to serve as anolyte, is used as construction material after filter residue drying；OH will be consumed simultaneously-Anode Liquid is recycled to cathodic region as catholyte.
3. sodium acid carbonate according to claim 1 makees the CO of basic nature agent2Mineralising electricity-generating method, it is characterised in that institute The alkaline solid waste stated is selected from least one of carbide slag, cement dust, incineration firing discarded object, slag, flyash.
4. sodium acid carbonate according to claim 1 makees the CO of basic nature agent2Mineralising electricity-generating method, it is characterised in that institute The alkaline solid waste stated is that CaO content is less than 50%, either less than 30% or less than 20%, preferably shorter than 10%, and be not 0% alkaline solid waste.
5. sodium acid carbonate according to claim 1 makees the CO of basic nature agent2Mineralising electricity-generating method, it is characterised in that CO2The temperature of mineralising cell reaction is 10~100 DEG C, preferably 35~45 DEG C, more preferably 40 DEG C.
6. sodium acid carbonate according to claim 1 makees the CO of basic nature agent2Mineralising electricity-generating method, it is characterised in that institute State supporting electrolyte and be selected from NaCl, NaHCO3、NaNO3、Na2SO4One kind in solution, preferred concentration are 0.5-5mol/L's NaCl solution.
7. sodium acid carbonate according to claim 1 makees the CO of basic nature agent2Mineralising electricity-generating method, it is characterised in that cloudy Pole electrode is metal platinum, Metal Palladium or porous electrode made of metallic nickel, and anode electrode is gas-diffusion electrode.
8. sodium acid carbonate according to claim 1 makees the CO2 mineralising electricity-generating methods of basic nature agent, it is characterised in that Anode region, the solution in cathodic region are stored using corresponding solution reservoir, and make solution in anode region, cathodic region by circulating pump Circulated between corresponding storage tank.
9. sodium acid carbonate according to claim 1 makees the CO of basic nature agent2Mineralising electricity-generating method, it is characterised in that CO2The mode for being passed through cathodic region uses independent carbon dioxide absorption tower, or by bubbling by CO2It is passed through in solution.
10. sodium acid carbonate according to claim 9 makees the CO of basic nature agent2Mineralising electricity-generating method, it is characterised in that By CO under 0.1-0.2Mpa2It is passed through cathodic region.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108736052A (en) * 2018-03-30 2018-11-02 四川大学 It is a kind of to enhance CO using riboflavin2The method and its battery of mineralising battery electricity generation performance
EP3771023A4 (en) * 2018-03-19 2021-12-15 GT Co., Ltd. Carbon dioxide utilization system, and complex power generation system comprising same
CN113930783A (en) * 2021-09-29 2022-01-14 四川大学 CO2Method and device for producing hydrogen by mineralizing solid waste power generation coupling

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CN104131311A (en) * 2014-07-07 2014-11-05 四川大学 Method utilizing CO2 mineralization to produce sodium bicarbonate or sodium carbonate and output electric energy
CN106299424A (en) * 2015-05-23 2017-01-04 李坚 A kind of alkalescence directly water CO2 fuel cell and application thereof

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CN104131311A (en) * 2014-07-07 2014-11-05 四川大学 Method utilizing CO2 mineralization to produce sodium bicarbonate or sodium carbonate and output electric energy
CN106299424A (en) * 2015-05-23 2017-01-04 李坚 A kind of alkalescence directly water CO2 fuel cell and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3771023A4 (en) * 2018-03-19 2021-12-15 GT Co., Ltd. Carbon dioxide utilization system, and complex power generation system comprising same
CN108736052A (en) * 2018-03-30 2018-11-02 四川大学 It is a kind of to enhance CO using riboflavin2The method and its battery of mineralising battery electricity generation performance
CN113930783A (en) * 2021-09-29 2022-01-14 四川大学 CO2Method and device for producing hydrogen by mineralizing solid waste power generation coupling

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