CN112522733B - Desulfurization fuel cell and method for producing acid and alkali cooperatively by flue gas desulfurization - Google Patents

Desulfurization fuel cell and method for producing acid and alkali cooperatively by flue gas desulfurization Download PDF

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Publication number
CN112522733B
CN112522733B CN202011401354.9A CN202011401354A CN112522733B CN 112522733 B CN112522733 B CN 112522733B CN 202011401354 A CN202011401354 A CN 202011401354A CN 112522733 B CN112522733 B CN 112522733B
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cathode
anode
chamber
desulfurization
channel
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CN112522733A (en
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吴旭
韦聚才
古月圆
吴怀德
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Hubei Huadelai Energy Saving And Emission Reduction Technology Co ltd
Huazhong University of Science and Technology
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Hubei Huadelai Energy Saving And Emission Reduction Technology Co ltd
Huazhong University of Science and Technology
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • 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
    • C25B1/16—Hydroxides
    • 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
    • C25B1/22—Inorganic acids
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • 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
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0675—Removal of sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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

Abstract

The invention provides a desulfurization fuel cell and a method for producing acid and alkali cooperatively by flue gas desulfurization, wherein the cell comprises the following components: the anode mechanism comprises an anode splitter plate, an anode and an anolyte chamber, and the anode splitter plate is communicated with the anolyte chamber; the cathode mechanism comprises a cathode flow distribution plate, a cathode, a gas chamber and a cathode electrolyte chamber, wherein a cathode electrolyte channel and a gas channel are formed in the cathode flow distribution plate; a diaphragm; according to the method for producing acid and alkali cooperatively by flue gas desulfurization, provided by the invention, sulfite and sulfide ions generate oxidation reaction on the surface of the anode to generate sulfate radicals and generate hydrogen ions at the same time, oxygen molecules generate oxygen reduction reaction on the surface of the cathode to generate hydroxyl radicals, the two can form a primary cell to release electric energy outwards, sulfuric acid generated by the anode can be recycled, and the recycling of the cathode alkali can be realized, so that one hundred percent of sulfur elements can be recycled.

Description

Desulfurization fuel cell and method for producing acid and alkali cooperatively by flue gas desulfurization
Technical Field
The invention relates to the technical field of electrochemical engineering application, in particular to a desulfurization fuel cell and a method for producing acid and alkali cooperatively by flue gas desulfurization.
Background
Sulfur dioxide (SO) 2 ) Is one of the main causes of acid rain and also one of the main causes of haze weather. China is a large country of fire coal, SO 2 Is always a key concern for preventing and controlling the atmospheric pollution in China. Currently, the predominant desulfurization process is the wet limestone-gypsum process, which, although addressing SO in the atmosphere 2 Pollution, but a large amount of desulfurized gypsum is generated, and new environmental pollution is caused. Moreover, the process system has large occupied area, easy scaling and blockage of pipelines, large abrasion to equipment and pipelines, need to be cleaned and maintained regularly, and have high one-time construction investment cost. Compared with a wet limestone-gypsum method, the sodium-alkali desulfurization technology is mature, the mass transfer rate is high, the absorption rate and the desulfurization rate are high, no waste water is discharged, no phenomena such as scaling and blockage are caused in the absorption process, and no secondary pollution is caused. However, sodium hydroxide, which is relatively costly, is used as a raw material in the sodium alkali process, and the desulfurization cost is relatively high. Therefore, development of a low-cost alkali preparation process is important for sodium-alkali desulfurization.
Based on the technical drawbacks of the current desulfurization process, improvements are needed.
Disclosure of Invention
In view of the above, the invention provides a desulfurization fuel cell and a method for producing acid and alkali cooperatively by flue gas desulfurization, which solve the technical defects in the prior art.
In a first aspect, the present invention provides a desulphurised fuel cell comprising:
the anode mechanism comprises an anode flow dividing plate, an anode and an anolyte chamber, wherein the anode is positioned between the anode flow dividing plate and the anolyte chamber, an anolyte channel is formed in the anode flow dividing plate, and the anode flow dividing plate is communicated with the anolyte chamber through the anolyte channel;
the cathode mechanism comprises a cathode flow distribution plate, a cathode, a gas chamber and a catholyte chamber, wherein the cathode is positioned between the gas chamber and the catholyte chamber, the gas chamber is positioned between the cathode flow distribution plate and the cathode, a catholyte channel and a gas channel are formed in the cathode flow distribution plate, the cathode flow distribution plate is communicated with the catholyte chamber through the catholyte channel, the cathode flow distribution plate is communicated with the gas chamber through the gas channel, and the gas chamber is communicated with the cathode;
a diaphragm positioned between the anolyte and catholyte chambers.
Optionally, the desulfurization fuel cell further comprises an anode current collector and a cathode current collector, wherein one side of the anode current collector is attached to an anode current distribution plate, the other side of the anode current collector is attached to the anode, and the anode current distribution plate is communicated with the anode electrolyte chamber through the anode electrolyte channel via the anode current collector;
one side of the cathode current collector is attached to the gas chamber, the other side of the cathode current collector is attached to the cathode, a hollow part corresponding to the gas chamber is arranged on the cathode current collector, the gas chamber is communicated with the cathode through the cathode current collector, and the cathode current distribution plate is communicated with the cathode electrolyte chamber through the cathode electrolyte channel through the cathode current collector.
Optionally, the desulfurization fuel cell is characterized in that the membrane is a cation exchange membrane or an anion exchange membrane.
Optionally, the anode of the desulfurization fuel cell comprises an anode substrate and an anode catalyst supported on the anode substrate, wherein the anode catalyst comprises one of platinum and its alloy, gold and its alloy, cobalt and its alloy, vanadium and its alloy, copper and its alloy, iron and its alloy, and a carbon-based catalyst.
Optionally, the desulfurization fuel cell further comprises a cathode catalyst supported on the cathode substrate, wherein the cathode catalyst comprises one of platinum and its alloys, gold and its alloys, cobalt and its alloys, nickel and its alloys, manganese and its alloys, and carbon-based catalyst.
Optionally, the anode electrolyte chamber and the cathode electrolyte chamber of the desulfurization fuel cell are both made of porous foam structural materials.
Optionally, the desulfurization fuel cell is attached to the cathode splitter plate, and the gas chamber attached to the cathode splitter plate may be assembled to the cathode splitter plate, i.e. the gas chamber is directly opened on the cathode splitter plate.
It will be appreciated that more complex series and parallel configurations of the battery configuration may be achieved by the combination of the arrangement of the anode and cathode mechanisms.
In a second aspect, the invention also provides a method for producing acid and alkali cooperatively by flue gas desulfurization, which comprises the following steps:
absorbing sulfur dioxide and hydrogen sulfide gas in the flue gas by using alkali liquor to obtain a solution containing sulfite and sulfide;
adding a solution containing sulfite and sulfide into the anolyte channel of the desulfurization fuel cell in any one of claims 1-6;
optionally, water or alkali liquor is added into the catholyte channel of the desulfurization fuel cell, and air or oxygen is introduced into the gas channel;
and conducting the cathode and the anode of the desulfurization fuel cell to enable the desulfurization fuel cell to self-discharge or apply external voltage to the desulfurization fuel cell, and preparing acid and alkali through electrochemical reaction.
Optionally, in the method for producing acid and alkali cooperatively by flue gas desulfurization, the alkali liquor is sodium hydroxide solution or potassium hydroxide solution.
Optionally, in the method for co-producing acid and alkali by flue gas desulfurization, alkali liquor is used for absorbing sulfur dioxide and hydrogen sulfide gas in flue gas, wherein the pH value of the alkali liquor is 11-14;
and adding water or alkali liquor into the catholyte channel of the desulfurization fuel cell, wherein the pH value of the alkali liquor is 7-14.
Optionally, in the method for producing acid and alkali cooperatively by flue gas desulfurization, the temperature of the added solution containing sulfite and sulfide is 5-80 ℃, and the temperature of the added solution containing sulfite and sulfide is 5-80 ℃.
Compared with the prior art, the method for producing acid and alkali cooperatively by desulfurizing fuel cells and flue gas has the following beneficial effects:
(1) The desulfurization fuel cell of the invention can realize stable self-discharge of the sulfite-air fuel cell, and is SO 2 The waste is changed into valuable, and more ways are provided;
(2) According to the method for producing acid and alkali cooperatively by flue gas desulfurization, provided by the invention, sulfite and sulfide ions generate oxidation reaction on the surface of an anode to generate sulfate radicals and generate hydrogen ions at the same time, oxygen molecules generate oxygen reduction reaction on the surface of a cathode to generate hydroxyl radicals, the hydrogen radicals and the oxygen molecules can form a primary cell to release electric energy outwards, sulfuric acid generated by the anode can be recycled, and the cathode alkali can be recycled, so that one hundred percent of sulfur elements can be recycled and reused, the desulfurization mass transfer rate is high, the absorption rate and the desulfurization rate are high, and no waste water is discharged in the whole process, and no secondary pollution is caused;
(3) The method for producing acid and alkali cooperatively by flue gas desulfurization can regenerate acid and alkali without cost; even if the applied voltage accelerates the reaction, the cost of producing alkali is still lower than the price of caustic soda and other medicaments.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is evident that the drawings in the following description are only some embodiments of the present invention and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is a schematic view of a desulfurizing fuel cell of the present invention;
FIG. 2 is a schematic view of the porous foam structure of the desulfurization fuel cell of the present invention;
FIG. 3 is a graph showing the discharge of a desulfurization fuel cell in the method for co-producing acid and alkali by flue gas desulfurization according to examples 1 to 3 of the present invention;
FIG. 4 is a graph showing the discharge of a desulfurization fuel cell in the methods of co-producing acid and alkali by flue gas desulfurization according to examples 1 and 4 of the present invention;
FIG. 5 is a graph showing the discharge of a desulfurization fuel cell in the method for co-producing acid and base by flue gas desulfurization in example 5 of the present invention;
FIG. 6 is a graph of constant current operating potential versus time for a desulfurization fuel cell in the flue gas desulfurization co-production of acid and base in example 6 of the present invention;
FIG. 7 is a graph of current versus potential for a desulfurized fuel in the flue gas desulfurization co-production of acid and base in examples 1, 7, 8, 9 of the present invention;
fig. 8 is a graph showing the current-potential curve of the desulfurized fuel in the method of the flue gas desulfurization co-production of acid and alkali in example 10 and example 11 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made in detail and with reference to the embodiments of the present invention, but it should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
A desulfurized fuel cell, as shown in fig. 1, comprising:
the anode mechanism comprises an anode flow dividing plate 1, an anode 3 and an anolyte chamber 4, wherein the anode 3 is positioned between the anode flow dividing plate 1 and the anolyte chamber 4, an anolyte channel 11 is formed in the anode flow dividing plate 1, and the anode flow dividing plate 1 is communicated with the anolyte chamber 4 through the anolyte channel 11;
the cathode mechanism comprises a cathode flow distribution plate 10, a gas chamber 9, a cathode 7 and a catholyte chamber 6, wherein the cathode 7 is positioned between the gas chamber 9 and the catholyte chamber 6, the gas chamber 9 is positioned between the cathode 7 and the cathode flow distribution plate 10, a catholyte channel 101 and a gas channel 102 are formed on the cathode flow distribution plate 10, the cathode flow distribution plate 10 is communicated with the catholyte chamber 6 through the catholyte channel 101, the cathode flow distribution plate 10 is communicated with the gas chamber 9 through the gas channel 102, and the gas chamber 9 is communicated with the cathode 7;
a diaphragm 5 located between the anolyte chamber 4 and the catholyte chamber 6.
It should be noted that, in the embodiment of the present application, the anode splitter plate 1 may be a cuboid plate body, one end of an anolyte channel 11 formed on the anode splitter plate is an inlet, the other end is an outlet, the anode splitter plate 1 is communicated with the anolyte chamber 4 through the anolyte channel 11, and a solution containing sodium sulfite and sodium sulfide can be introduced into the anolyte chamber 4 through the anolyte channel 11, and meanwhile, sulfuric acid products can be derived; in practice, the anode splitter plate 1 may take other forms, for example, may be a box body with a hollow interior, and an inlet and an outlet are provided to introduce a solution containing sodium sulfite and sodium sulfide into the anode electrolyte chamber 4; the anolyte chamber 4 is of a hollow cavity structure, the anode 3 is positioned between the anode splitter plate 1 and the anolyte chamber 4, and the inside of the anolyte chamber 4 is communicated with the anode 3; in operation, the sodium sulfite, sodium sulfide containing solution in the anode manifold 1 flows through the anolyte passageway 11 into the anolyte chamber 4 and then to the surface of the anode 3 and an anodic reaction occurs at the surface of the anode 3. Correspondingly, the cathode flow distribution plate 10 can also be a cuboid plate body, the cathode flow distribution plate 10 is provided with a cathode electrolyte channel 101, one end of the cathode electrolyte channel 101 is an inlet, the other end is an outlet, the cathode flow distribution plate 10 is communicated with the cathode electrolyte chamber 6 through the cathode electrolyte channel 101, and alkali liquor in the cathode electrolyte chamber 6 can be discharged through the cathode electrolyte channel 101; obviously, the cathode splitter plate 9 can take other forms, such as a box body with a hollow interior, and an inlet and an outlet are arranged to feed alkaline solution into the catholyte chamber 6; further, the cathode splitter plate 10 is also provided with a gas channel 102, the gas channel 102 is communicated with the gas chamber 9, air or oxygen can be introduced into the gas chamber 9 through the gas channel 102, and the gas chamber 9 is communicated with the cathode 7; specifically, the gas chamber 9 has a hollow chamber structure, that is, a through hole can be formed in the gas chamber 9, the cathode 7 can be attached to the hole, meanwhile, a through hole 91 is formed in the gas chamber 9, and the through hole 91 is communicated with the catholyte channel 101; air or oxygen is introduced through the gas channel 102, reaches the surface of one side of the cathode 7 through the gas chamber 9, and then the cathode reaction occurs; specifically, the catholyte chamber 6 is a hollow chamber structure, the cathode 7 is positioned between the gas chamber 9 and the catholyte chamber 6, and the other side surface of the cathode 7 is communicated with the inside of the catholyte chamber 6; when the cathode electrolyte device works, alkaline liquor in the cathode electrolyte chamber 6 can be introduced into the gas chamber 9 through the through hole 91 by the cathode electrolyte channel 101, oxygen or air is introduced into the gas chamber 9 through the gas channel 102, the oxygen or air reacts in the catalytic layer of the cathode 7, and hydrogen and oxygen generated by the reaction enter the cathode electrolyte chamber 6 to generate alkaline liquor; a diaphragm 5 is positioned between anolyte and catholyte chambers 4 and 6 for separating the anolyte and catholyte, and a particular diaphragm 5 may employ an ion-exchange membrane to transport specific ions.
In some embodiments, the gas chambers attached to the cathode manifold 10 may be integrated onto the cathode manifold 10, i.e., the gas chambers may be opened directly onto the cathode manifold 10.
In some embodiments, the anode current collector 2 and the cathode current collector 8 are further included, one side of the anode current collector 2 is attached to the anode current collector 1, the other side of the anode current collector 2 is attached to the anode 3, and the anode current collector 1 is communicated with the anolyte chamber 4 through the anolyte channel 11 via the anode current collector 2;
one side of the cathode current collector 8 is attached to the gas chamber 9, the other side is attached to the cathode 7, the position, corresponding to the gas chamber 9, on the cathode current collector 8 is provided with a hollow 82, the gas chamber 9 is communicated with the cathode 7 through the cathode current collector 8, and the cathode current distribution plate 10 is communicated with the cathode electrolyte chamber 6 through the cathode current collector 8 through the cathode electrolyte channel 101.
Specifically, in the embodiment of the present application, the materials of the anode current collector 2 and the cathode current collector 8 may be stainless steel, titanium alloy, etc., and the anode current collector 2, the anode 3 and the anolyte chamber 4 are sequentially attached to each other; specifically, in the embodiment of the present application, the specific structure of the anolyte chamber 4 is: the anolyte chamber 4 can be a rectangular block body, a through hole is formed in the anolyte chamber 4, the anode 3 is matched with the through hole in the anolyte chamber 4, one side of the anode 3 is attached to the through hole, the other side of the anode 3 is attached to the anode current collector 2, the area of the anode 3 is smaller than that of the anode current collector 4, the anode current collector 2 is provided with a through hole 21, an anolyte channel 11 formed in the anode current distribution plate 1 is communicated with the through hole 21, and when in operation, a solution containing sodium sulfite and sodium sulfide in the anode current distribution plate 1 flows into the anolyte chamber 4 through the anolyte channel 11 and the through hole 21, then reaches the surface of the anode 3, and anode reaction occurs on the surface of the anode 3; the cathode flow dividing plate 10, the gas chamber 9, the cathode current collector 8, the cathode 7 and the catholyte chamber 6 are sequentially attached; the joint of the cathode current collector 8 corresponding to the cathode 7 is in a hollow structure; the specific structure of the catholyte chamber 6 is: the catholyte chamber 6 may be a rectangular block body, through holes are formed in the rectangular block body, one side of the cathode 7 is attached to the hollow 82 of the cathode current collector 8, the other side of the cathode 7 is attached to the through holes on the catholyte chamber 6, the hollow position of the cathode current collector 8 corresponds to the gas chamber 9, and air or oxygen introduced into the gas channel 102 enters the gas chamber 9 and reaches the surface of the cathode 7 through the hollow 82 of the cathode current collector 8; simultaneously, a perforation 81 is formed on the cathode current collector 8, the perforation 81 is communicated with the catholyte channel 101, alkali liquor or water introduced into the catholyte channel 101 flows into the catholyte chamber 6 through the perforation 81, when the cathode current collector works, air or oxygen introduced into the gas channel 102 reaches the surface of the cathode 7 through the gas chamber 9 and the hollowed-out part of the cathode current collector 8, and the alkali liquor or water is added into the catholyte chamber 6 through the cathode current collector 8 to carry out cathode reaction. In practice, the electrochemical reaction of the anode and the cathode is realized by connecting the anode current collector 2 and the cathode current collector 8 to the positive electrode and the negative electrode of the power supply, respectively.
In some embodiments, the membrane 5 is a cation exchange membrane or an anion exchange membrane. The cation exchange membrane can be Nafion N117, fumasep cube FKD-PK-75, hoCM G-1201 and the like; the anion exchange membrane can be Fumasep cube FAA-3-PK-75, hoAM G-1204, AMI A-701, etc., i.e. the membrane 6 is an ion exchange membrane which can allow specific cations (Na + ) Or anions (SO) 4 2- ) Through the device.
In some embodiments, the anode 3 comprises an anode substrate and an anode catalyst supported on the anode substrate, the anode catalyst comprising one of platinum and its alloys, gold and its alloys, cobalt and its alloys, vanadium and its alloys, copper and its alloys, iron and its alloys, carbon-based catalysts; specifically, the anode substrate may be a hydrophilic substrate carbon cloth, and the anode catalyst may be a carbon-supported platinum catalyst.
In some embodiments, the cathode 7 comprises a cathode substrate and a cathode catalyst supported on the cathode substrate, the cathode catalyst comprising one of platinum and its alloys, gold and its alloys, cobalt and its alloys, nickel and its alloys, manganese and its alloys, carbon-based catalysts.
In the embodiment of the present application, the anode catalyst on the anode substrate and the cathode catalyst on the cathode substrate are disposed toward the separator 5.
In some embodiments, anolyte compartment 4 and catholyte compartment 6 are each fabricated from a porous foam structure material. As shown in fig. 2, the porous foam structure can make the liquid and gas distribution more uniform, improve, and increase the current.
It will be appreciated that this solution only shows basic cells, and that more complex series and parallel configurations of the battery structure can be achieved by the combination of the arrangement of the anode and cathode means.
Based on the same conception, the application also provides a method for producing acid and alkali cooperatively by flue gas desulfurization, which adopts the desulfurization fuel cell, and comprises the following steps:
s1, absorbing sulfur dioxide and hydrogen sulfide gas in the flue gas by using alkali liquor to obtain a solution containing sulfite and sulfide;
s2, adding a solution containing sulfite and sulfide into an anolyte channel of the desulfurization fuel cell;
s3, adding water or alkali liquor into a cathode electrolyte channel of the desulfurization fuel cell, and simultaneously introducing air or oxygen into a gas channel;
and S4, conducting the cathode and the anode of the desulfurization fuel cell to enable the desulfurization fuel cell to self-discharge or apply external voltage to the desulfurization fuel cell, and preparing acid and alkali through electrochemical reaction.
In the embodiment of the present application, applying an external voltage to the desulfurization fuel cell means that an anode or an anode current collector is connected to a power source anode, and a cathode or a cathode current collector is connected to a power source cathode, and the electrochemical reaction that occurs is that:
the cathode reaction is as follows:
cell reaction:
from the above, the sulfite and the sulfide ions generate the sulfate radical on the surface of the anode and generate hydrogen ions at the same time, and the oxygen molecules generate the hydroxyl radical on the surface of the cathode through the oxygen reduction reaction, so that the two can form the primary battery to release electric energy outwards. In actual use, after sulfite and sulfide ions are completely converted, the generated alkali liquor can be recycled to the step S1 for recycling of sulfuric acid.
In some embodiments, the lye in S1 and S3 is sodium hydroxide solution or potassium hydroxide solution.
In some embodiments, the pH of the lye in S1 is 11-14; and S3, the pH value of the alkali liquor in the step S is 7-14.
In some embodiments, the temperature of the added solution containing sulfite and sulfide is 5-80 ℃, the temperature of the added water or alkali solution is 5-80 ℃, and the temperature of the operating environment of the flue gas desulfurization synergistic acid-base generating method is 5-80 ℃.
The flue gas desulfurization co-acid and alkali production method of the present application is further described in the following specific examples.
Example 1
In the embodiment of the application, the desulfurization Fuel cell includes an anode current collector 2 and a cathode current collector 8, the used membrane 5 is a cation exchange membrane Nafion N117, the anode substrate is hydrophilic carbon cloth (TGP-H-090, japan), the anode catalyst is a carbon-supported platinum catalyst (20 wt% Fuel cell Store), the cathode is a hydrophobic carbon cloth electrode which is purchased from the Fuel cell Store and carries 20 wt% Pt/C, the anolyte chamber 4 and the catholyte chamber 6 are made of acrylic materials into hollow materials, and do not have a porous foam structure, and the specific method for flue gas desulfurization and co-production of acid and alkali is as follows:
s1, absorbing sulfur dioxide and hydrogen sulfide gas in the flue gas by using a sodium hydroxide solution with the pH value of 11 to obtain a solution containing sulfite and sulfide;
s2, adding a solution containing sulfite and sulfide into an anolyte channel of the desulfurization fuel cell at room temperature;
s3, adding 0.5mol/L sodium hydroxide solution into a catholyte channel of the desulfurization fuel cell, and simultaneously introducing air into a gas channel;
and S4, conducting the cathode and the anode of the desulfurization fuel cell to enable the desulfurization fuel cell to self-discharge, and preparing acid and alkali through electrochemical reaction.
The temperature of the added solution containing sulfite and sulfide is 40 ℃, the temperature of the added sodium hydroxide solution is 40 ℃, namely the temperature of the operating environment of the method for producing acid and alkali by the flue gas desulfurization is 40 DEG C
Example 2
The method for co-producing acid and alkali by flue gas desulfurization provided in the embodiment of the application is the same as that in embodiment 1, except that a sodium hydroxide solution with a pH of 13 is used in S1.
Example 3
The method for co-producing acid and alkali by flue gas desulfurization provided in the embodiment of the application is the same as that in embodiment 1, except that a sodium hydroxide solution with a pH of 14 is used in S1.
Example 4
The method for co-producing acid and alkali by flue gas desulfurization provided by the embodiment of the application is different from the method in embodiment 1 in that a potassium hydroxide solution with pH of 11 is used in S1, and a potassium hydroxide solution with the concentration of 0.5mol/L is used in S3.
Example 5
The method for co-producing acid and alkali by flue gas desulfurization provided in the embodiment of the application is different from the method in embodiment 1 in that the molar concentration of the sodium hydroxide solution in S3 is replaced by 0.1mol/L, 0.25mol/L, 0.75mol/L, 1mol/L and 0mol/L (0 mol/L means adding pure water).
Example 6
The method for co-producing acid and alkali by flue gas desulfurization provided by the embodiment of the application is different from the method in embodiment 1 in that the self-discharge of the sulfur fuel cell is changed into an external power supply and the sulfur fuel cell works under constant current, and the specific constant current is 0, 5, 10, 20, 50 and 100 milliamperes per square centimeter respectively.
Example 7
The method for producing acid and alkali cooperatively by flue gas desulfurization is different from the method in embodiment 1 in that the used membrane 5 is an anion exchange membrane, and the anion exchange membrane adopts Fumasep FAA-3-PK-75.
Example 8
The method for co-producing acid and alkali by flue gas desulfurization provided by the embodiment of the application is different from the method in embodiment 1 in that the anode catalyst is a cobaltosic oxide catalyst.
Example 9
The method for collaborative acid and alkali production by flue gas desulfurization provided by the embodiment of the application is different from the embodiment 1 in that the anode catalyst is a gold-copper alloy catalyst and the cathode catalyst is a nickel-cobalt-manganese ternary oxide catalyst.
Example 10
The method for producing acid and alkali by flue gas desulfurization in a synergistic manner provided by the embodiment of the application is different from the method in embodiment 1 in that the temperature of the added solution containing sulfite and sulfide is 5 ℃, the temperature of the added sodium hydroxide solution is 5 ℃, and the temperature of the operating environment of the method for producing acid and alkali by flue gas desulfurization in a synergistic manner is 5 ℃.
Example 11
The method for producing acid and alkali cooperatively by flue gas desulfurization provided by the embodiment of the application is different from the method in embodiment 1 in that the temperature of the added solution containing sulfite and sulfide is 80 ℃, the temperature of the added sodium hydroxide solution is 80 ℃, and the temperature of the operating environment of the method for producing acid and alkali cooperatively by flue gas desulfurization is 80 ℃.
The discharge curve of the desulfurization fuel cell in the method for co-producing acid and alkali by flue gas desulfurization in the above embodiments 1 to 3 is tested, and the result is shown in fig. 3, and it is known from fig. 3 that the pH of the sodium hydroxide solution is in the range of 11 to 14, and there is no obvious influence on the performance of the desulfurization fuel cell, that is, no obvious influence on the regenerated acid and alkali of the desulfurization fuel cell.
The discharge curves of the desulfurization fuel cells in the methods for the co-production of acid and alkali by the flue gas desulfurization in the above examples 1 and 4 are tested, and the results are shown in fig. 4. As can be seen from fig. 4, the effect of using potassium hydroxide solution and sodium hydroxide solution is similar, so that the flue gas can be rapidly and efficiently desulfurized, and the fuel cell can regenerate acid and alkali at low cost.
The discharge curve of the desulfurization fuel cell in the method of the flue gas desulfurization co-production of acid and alkali in the above example 5 was tested, and the result is shown in fig. 5. It can be seen from fig. 5 that the sodium hydroxide concentration has a significant effect on the performance of the fuel cell, and when the sodium hydroxide concentration is 0.5mol/l, the cell discharge current can break through 20 milliamp/square centimeter, and when the sodium hydroxide concentration is 0mol/l, i.e., pure water, the fuel cell open circuit is 0.94V, which is similar to that of the conventional oxyhydrogen fuel cell.
The constant current operating potential-time curve of the desulfurization fuel in the flue gas desulfurization co-production of acid and alkali in example 6 was tested, and the result is shown in fig. 6. It is known from fig. 6 that when the discharge current is less than 20 milliamperes per square centimeter, the fuel cell can discharge electric energy to the outside, and the operation cost of acid production and alkali production is zero. In order to accelerate the reaction rate, the external power supply leads the current of the battery to reach 100 milliamperes per square centimeter, the external voltage is only 0.67 and V at the moment, the production cost of sodium hydroxide is only 900 kilowatt-hours per ton, and the electricity price is 0.7 yuan per kilowatt-hour, namely 630 yuan per ton, which is far lower than the market selling price (3500-4100 yuan) of sodium hydroxide.
The current-potential curves of the desulfurized fuel in the methods of flue gas desulfurization co-production of acid and alkali in examples 1, 7, 8 and 9 were tested, and as shown in fig. 7, it is understood from fig. 7 that the desulfurized fuel cell exhibited excellent performance similar to that of example 6.
The current-potential curves of the desulfurization fuel in the methods of the flue gas desulfurization co-production of acid and alkali in example 10 and example 11 were tested, and the results are shown in fig. 8, and it is clear from fig. 8 that the desulfurization fuel cell can still operate normally at a low temperature of 5 ℃, and the discharge current density reaches 45 milliamperes per square centimeter at 80 ℃.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (1)

1. The method for producing acid and alkali cooperatively by flue gas desulfurization is characterized by comprising the following steps:
absorbing sulfur dioxide and hydrogen sulfide gas in the flue gas by using a sodium hydroxide solution with the pH of 11 to obtain a solution containing sulfite and sulfide;
adding a solution containing sulfite and sulfide to an anolyte channel of a desulfurization fuel cell at room temperature;
adding 0.5mol/L sodium hydroxide solution into a cathode electrolyte channel of the desulfurization fuel cell, and simultaneously introducing air into a gas channel;
conducting the cathode and the anode of the desulfurization fuel cell to enable the desulfurization fuel cell to self-discharge, and preparing acid and alkali through electrochemical reaction;
the temperature of the added solution containing sulfite and sulfide is 40 ℃, and the temperature of the added sodium hydroxide solution is 40 ℃; namely, the temperature of the operation environment of the method for producing acid and alkali cooperatively by flue gas desulfurization is 40 ℃;
the desulfurization fuel cell includes:
the anode mechanism comprises an anode flow dividing plate, an anode and an anolyte chamber, wherein the anode is positioned between the anode flow dividing plate and the anolyte chamber, an anolyte channel is formed in the anode flow dividing plate, and the anode flow dividing plate is communicated with the anolyte chamber through the anolyte channel;
the cathode mechanism comprises a cathode flow distribution plate, a cathode, a gas chamber and a catholyte chamber, wherein the cathode is positioned between the gas chamber and the catholyte chamber, the gas chamber is positioned between the cathode flow distribution plate and the cathode, a catholyte channel and a gas channel are formed in the cathode flow distribution plate, the cathode flow distribution plate is communicated with the catholyte chamber through the catholyte channel, the cathode flow distribution plate is communicated with the gas chamber through the gas channel, and the gas chamber is communicated with the cathode;
a diaphragm positioned between the anolyte chamber and the catholyte chamber;
the anode current collector is attached to the anode current collector through the anode electrolyte channel, and the anode current collector is communicated with the anode electrolyte chamber through the anode current collector;
one side of the cathode current collector is attached to the gas chamber, the other side of the cathode current collector is attached to the cathode, a hollow part corresponding to the gas chamber is arranged on the cathode current collector, the gas chamber is communicated with the cathode through the cathode current collector, and the cathode current distribution plate is communicated with the cathode electrolyte chamber through the cathode electrolyte channel through the cathode current collector;
the diaphragm is a cation exchange membrane Nafion N117;
the anode comprises an anode substrate and an anode catalyst supported on the anode substrate;
the anode substrate is hydrophilic carbon cloth, and is arranged in the east of Japan, and TGP-H-090;
the anode catalyst is a carbon-supported platinum catalyst, 20 wt% Fuel cell store;
the cathode was a 20 wt% Pt/C loaded hydrophobic carbon cloth electrode from Fuel cell Store.
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