CN114411166B - Device and method for membrane electrolysis hydrogen production combined carbon dioxide trapping - Google Patents
Device and method for membrane electrolysis hydrogen production combined carbon dioxide trapping Download PDFInfo
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- CN114411166B CN114411166B CN202210020214.XA CN202210020214A CN114411166B CN 114411166 B CN114411166 B CN 114411166B CN 202210020214 A CN202210020214 A CN 202210020214A CN 114411166 B CN114411166 B CN 114411166B
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- 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
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- 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
- B01D53/62—Carbon oxides
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- 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
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- 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
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
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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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
Abstract
The invention discloses a device and a method for membrane electrolysis hydrogen production and carbon dioxide trapping, wherein the device comprises the following components: a dust removal facility; the electrolytic cell is provided with a cation passing membrane and an anion passing membrane which are separated from each other, and the cation passing membrane and the anion passing membrane divide the electrolytic cell into three cell chambers which are respectively a cathode electrolytic cell, an intermediate cell and an anode electrolytic cell; the cathode electrolytic cell is provided with a dust-removing flue gas/air inlet; the anode electrolytic tank is respectively provided with an oxygen collection port and a water supplementing port; a compressor in communication with the cathode electrolyzer; the electrolysis device comprises a power supply, a cathode and an anode, wherein the cathode and the anode are connected with the power supply, the cathode is arranged in a cathode electrolysis tank, and the anode is arranged in an anode electrolysis tank; and the first three-way valve is respectively communicated with the cathode electrolytic tank, the middle tank and the anode electrolytic tank and is used for controlling the communication and the sealing of the three tank chambers. The invention utilizes the electrolyzed water to generate oxygen and green energy hydrogen, and can fully and reasonably utilize the energy supplemented in the solvent regeneration process.
Description
Technical Field
The invention relates to the technical field of carbon dioxide trapping, in particular to a device and a method for combining membrane electrolysis hydrogen production with carbon dioxide trapping.
Background
With the development of world industry economy, resources and environmental problems caused by carbon emissions. There is a worldwide widespread concern, and carbon dioxide has been shown to be a major cause of global warming. To cope with global climate change, the reduction of carbon emissions has become a new consensus worldwide and a "new normalcy" of world economy. Based on the above, china also proposes a carbon peak and carbon neutralization '3060' target. The first step in achieving this is the capture and separation of carbon dioxide; meanwhile, along with the development of hydrogen energy, the technology of hydrogen production by water electrolysis is one of the main ways of obtaining hydrogen.
However, the existing carbon dioxide trapping process is complex in process and strict in application condition, meanwhile, the trapping of the flue gas is always a difficult point due to the fact that sulfur dioxide and particulate matters in the flue gas are used as main impurities, the concentration of the flue gas and the like, and meanwhile, the large amount of energy in the regeneration process is also one of the reasons for restricting the development of the carbon trapping technology; meanwhile, the current water electrolysis hydrogen production process generally mainly aims at producing hydrogen, and the potential of solution change existing in the electrolysis process cannot be fully utilized.
Disclosure of Invention
In view of the above, the present invention aims to provide a device and a method for combining membrane-process electrolytic hydrogen production with carbon dioxide capture, which can fully utilize the potential of solution variation in the electrolytic process.
The adopted technical scheme is as follows:
the invention relates to a device for membrane electrolysis hydrogen production and carbon dioxide trapping, which comprises:
the dust removal facility is used as a pretreatment link before flue gas/air enters the electrolytic cell;
the electrolytic cell is provided with a cation passing membrane and an anion passing membrane which are separated from each other, the cation passing membrane and the anion passing membrane divide the electrolytic cell into three cell chambers, and the three cell chambers are a cathode electrolytic cell, an intermediate cell and an anode electrolytic cell respectively; the cathode electrolytic cell is provided with a flue gas/air inlet; the flue gas/air inlet is communicated with the dust removing facility; the anode electrolytic tank is respectively provided with an oxygen collection port and a water supplementing port;
a compressor in communication with the catholyte tank;
an electrolysis device comprising a power source, a cathode connected to the power source, and an anode, the cathode being disposed in a cathode electrolyzer, the anode being disposed in an anode electrolyzer;
a first three-way valve which is respectively communicated with the cathode electrolytic tank, the intermediate tank and the anode electrolytic tank and is used for controlling the communication and the closure of the cathode electrolytic tank, the intermediate tank and the anode electrolytic tank;
and the third three-way valve is communicated with the front of the dust removing facility and is used for controlling the entering time of the smoke/air.
Further, the flue gas/air needs to be pretreated by a dust removal facility before entering the catholyte tank.
Further, the flue gas/air inlet is provided at the bottom end of the cathode electrolytic cell.
Further, the compressor is communicated with the top end of the cathode electrolytic tank through a second three-way valve.
Further, the water supplementing port is arranged at the bottom end of the side face of the anode electrolytic tank, and the water supplementing port is provided with a first valve.
Further, the oxygen collection port is arranged at the top end of the anode electrolytic tank, and the oxygen collection port is provided with a second valve.
The method for preparing hydrogen by membrane electrolysis and collecting carbon dioxide by combining the method comprises the following steps of:
s1, the same electrolyte solution: the cathode electrolytic tank, the intermediate tank and the anode electrolytic tank are all electrolyte solutions formed by single or compound active metal ions and strong acid roots;
s2, electrolysis: under the electrolysis action of a power supply, oxygen is generated in the anode electrolytic tank, and meanwhile, the solution becomes an acidic environment; generating hydrogen in the cathode electrolytic tank, and changing the solution into alkaline environment;
s3, carbon dioxide absorption: the flue gas is introduced after dust removalIn the cathode electrolytic tank, CO in the flue gas 2 And SO 2 Is absorbed by alkaline solution in the cathode electrolytic tank until absorption is saturated, and the smoke and CO are stopped being introduced 2 And SO 2 Formation of HCO respectively 3 - And SO 3 2- After the absorption is saturated, the method enters a step S4 for sulfur dioxide oxidation;
s4, oxidizing sulfur dioxide: air is blown into the cathode electrolytic tank, and SO is carried out by oxygen 3 2- Oxidation to SO 4 2-
Dissolving in electrolyte to make SO in fume 2 Is completely absorbed;
s5, releasing carbon dioxide, namely opening a first three-way valve to enable the three groove chambers to be communicated, reacting the solution and releasing the carbon dioxide.
Further, the method for combining the membrane method with the electrolytic hydrogen production and the carbon dioxide trapping further comprises S6, circulation: the first three-way valve is closed, electrolysis in step S2 is started, and steps S2-S5 are circulated.
The invention has the beneficial effects that:
the invention solves the problems of large energy supplement, large influence by impurities such as particles, sulfur dioxide and the like in the regeneration process of the existing carbon trapping technology, and simultaneously can fully and reasonably utilize the potential of solution change in the hydrogen production process of electrolyzed water, namely, by utilizing the electrolysis technology, acid and alkali solutions are generated under the action of positive ions passing through a membrane and negative ions passing through the membrane, and the alkaline solution adsorbs the flue gas (carbon dioxide and sulfur dioxide) after dust removal, and then fixes the sulfur dioxide in the flue gas in an electrolytic cell in an air oxidation mode, and then neutralizes the acidic solution generated by the anode environment, thereby releasing the carbon dioxide. Because the regeneration of the acid-base solution is completed in an electrolysis environment, in the process, green energy hydrogen is generated, and the energy input in the regeneration process is fully and reasonably utilized.
Drawings
FIG. 1 is a schematic diagram of a device for membrane process electrolysis hydrogen production in combination with carbon dioxide capture.
In FIG. 1, a 1-compressor; 2-cation passing through the membrane; 3-anions pass through the membrane; 4-cathode electrolyzer; 5-an intermediate tank; 6-an anodic electrolytic cell; 7-a dust removal facility; 8-an oxygen collection port; 9-water supplementing port; 10-a first valve; 11-a second three-way valve; 12-power supply; 13-cathode; 14-an anode; 15-a first three-way valve; 16-a second valve; 17-a third three-way valve.
Detailed Description
The present invention will be described in detail by way of specific examples, but the purpose and purpose of these exemplary embodiments are merely to illustrate the present invention, and do not constitute any limitation to the actual scope of the present invention in any way.
Referring to fig. 1, an apparatus for combined membrane process electrolytic hydrogen production and carbon dioxide capture in this embodiment includes a dust removal facility 7, an electrolytic cell, a compressor 1, an electrolysis apparatus, and a first three-way valve.
And a dust removal facility 7, wherein the dust removal facility 7 is used as a pretreatment link before flue gas/air enters the electrolytic cell.
The electrolytic cell is provided with a cation passing membrane 2 and an anion passing membrane 3 which are spaced, the cation passing membrane 2 and the anion passing membrane 3 divide the electrolytic cell into three cell chambers, and the three cell chambers are respectively a cathode electrolytic cell 4, an intermediate cell 5 and an anode electrolytic cell 6; the cathode electrolytic cell is provided with a flue gas/air inlet; the flue gas/air inlet is communicated with a dust removing facility 7; the cathode electrolytic tank 4 is connected with a dust removing device 7, and the outlet of the dust removing device can be arranged at the bottom end of the cathode electrolytic tank 4. The flue gas/air needs to be pretreated by a dust removal facility before entering the cathode electrolytic cell to remove particulate matters in the flue dust.
The anode electrolytic tank 6 is respectively provided with an oxygen collection port 8 and a water supplementing port 9; preferably, the water supplementing port 9 is arranged at the bottom end of the side face of the anode electrolytic tank 6, and the water supplementing port 9 is provided with a first valve 10. Preferably, an oxygen collection port 8 is provided at the top end of the anolyte tank 6, and the oxygen collection port 9 is provided with a second valve 16.
A compressor 1, a compressor 10 communicating with the cathode electrolyzer 4; it may be preferable that the compressor 10 communicates with the top end of the cathode electrolytic tank 4 through a second three-way valve 11.
An electrolysis apparatus comprising a power source 12, a cathode 13 and an anode 14 connected to the power source 12, the cathode 13
Placed in the catholyte tank 4 and the anode 14 placed in the anolyte tank 6;
a first three-way valve 15, which is respectively communicated with the cathode electrolytic tank, the intermediate tank and the anode electrolytic tank, for controlling the communication and closure of the cathode electrolytic tank, the intermediate tank and the anode electrolytic tank.
A third three-way valve 17, which is located before the dust-removing facility, controls the timing of the air/flue gas entering the dust-removing facility.
The device for the membrane electrolysis hydrogen production combined carbon dioxide trapping has the following functions:
1. a compressor: the hydrogen/carbon dioxide is collected under pressure.
2. A second three-way valve: and controlling the residual flue gas emission and the collection time of hydrogen and carbon dioxide collection.
3. And (3) a power supply: and (5) inputting energy of an electrolysis reaction.
4. Cation passes through the membrane: cations pass into the catholyte tank, balancing the ions.
5. The anions pass through the membrane: anions balance the ions by entering the anolyte cell.
6. Oxygen collection port: collecting oxygen generated by the anode.
7. And (3) water supplementing port: the system is replenished with water, replenishing water lost by electrolysis.
By using the device for membrane electrolysis hydrogen production and carbon dioxide trapping, one embodiment of the invention is that
The method for producing hydrogen by electrolyzing water and collecting carbon dioxide comprises the following steps:
s1, the same electrolyte solution: the cathode electrolytic tank, the intermediate tank and the anode electrolytic tank are all electrolyte solutions formed by single or compound active metal ions and strong acid roots; active metal ions such as Na + ,K + Strong acid radicals such as Cl - ,NO 3 - 。
S2, electrolysis: under the electrolysis action of a power supply, oxygen is generated in the anode electrolytic tank, and meanwhile, the solution becomes an acidic environment; generating hydrogen in the cathode electrolytic tank, and changing the solution into alkaline environment; specific:
anodic electrolytic reaction: h 2 O＝1/2O 2 +2H + +2e, the solution becoming an acidic environment;
cathode electrolytic reaction: 2H (H) 2 O+2e＝H 2 +2OH - The solution becomes alkaline.
S3, dedusting: the flue gas passes through the dust removal facility, gets rid of the particulate matter in the flue gas, prevents the influence to follow-up carbon dioxide entrapment.
S4, absorbing carbon dioxide/sulfur dioxide: introducing the flue gas after dust removal into a cathode electrolytic tank, absorbing carbon dioxide/sulfur dioxide by an alkaline solution, and entering a step S5 for sulfur dioxide oxidation after absorption saturation; specific:
the reaction of carbon dioxide absorbed by the alkaline solution is as follows: CO 2 +OH - ＝HCO 3 - 。
The reaction of sulfur dioxide absorbed by the alkaline solution is as follows: SO (SO) 2 +OH - →S0 3 2- +H2O
S5, oxidizing sulfur dioxide: introducing air into a cathode reaction tank after passing through a dust removal facility, and utilizing oxygen to remove SO 3 2- Oxidation to SO 4 2- Dissolving in electrolyte to make SO in fume 2 Is completely absorbed;
s6, releasing carbon dioxide, namely opening a first three-way valve to enable the three groove chambers to be communicated, reacting the solution and releasing the carbon dioxide; specific:
the reaction of the dissolved carbon dioxide release is as follows: h + +HCO 3 - ＝CO 2 +H 2 O。
S7, circulation: the first three-way valve is closed, electrolysis in step S2 is started, and steps S2-S6 are circulated.
The invention adopts the main principle that the electrolytic water is utilized to generate oxygen and green energy hydrogen, and the energy supplemented in the solvent regeneration process is fully and reasonably utilized, so that the influence of particulate matters and sulfur dioxide on the carbon capture process is avoided. Has the following advantages:
1. the reaction process is simple and convenient to realize.
2. The cyclic process generates green energy hydrogen.
3. The negative and positive electrolytic solution is prevented from being directly contacted by the negative and positive ion film, and ions of the balance electrolytic cell are supplemented.
4. The electrolysis process can utilize green electricity (solar power generation/wind power generation and the like), so that the problems of large-scale and long-period renewable energy waste electricity consumption at present are solved while the indirect carbon dioxide emission in the regeneration process is avoided.
5. The neutralization reaction process releases heat, which is more favorable for the analysis of carbon dioxide.
6. The potential of solution change existing in the hydrogen production process by water electrolysis is reasonably utilized.
7. And absorbing and resolving carbon dioxide by utilizing the solution acid-base alternation process.
8. The carbon dioxide is captured and connected with the hydrogen production process of the electrolyzed water.
9. The electrolyte is always in the solution system, and the solution can be ensured only by supplementing the water lost in the electrolytic process
The system is stable.
10. The influence of particulate matters and sulfur dioxide on a system in the carbon dioxide capturing process is solved.
The first, second, third, etc. in the present specification are for distinguishing components or parts having the same function or structure from each other, and do not include any sequential parts, and are not shown or described with relative importance. The corresponding components or parts are relatively independent, such as a first valve and a second valve; and further, a first three-way valve, a second three-way valve and a third three-way valve.
The above list of detailed descriptions is only specific to practical embodiments of the present invention, and they are not intended to limit the scope of the present invention, and all equivalent embodiments or modifications that do not depart from the spirit of the present invention should be included in the scope of the present invention.
Claims (7)
1. An apparatus for membrane process electrolysis hydrogen production in combination with carbon dioxide capture, comprising:
the dust removal facility is used as a pretreatment link before flue gas/air enters the electrolytic cell;
the electrolytic cell is provided with a cation passing membrane and an anion passing membrane which are separated from each other, the cation passing membrane and the anion passing membrane divide the electrolytic cell into three cell chambers, and the three cell chambers are a cathode electrolytic cell, an intermediate cell and an anode electrolytic cell respectively; the cathode electrolytic cell is provided with a flue gas/air inlet; the flue gas/air inlet is communicated with the dust removing facility; the anode electrolytic tank is respectively provided with an oxygen collection port and a water supplementing port;
a compressor in communication with the catholyte tank;
an electrolysis device comprising a power source, a cathode connected to the power source, and an anode, the cathode being disposed in a cathode electrolyzer, the anode being disposed in an anode electrolyzer;
a first three-way valve which is respectively communicated with the cathode electrolytic tank, the intermediate tank and the anode electrolytic tank and is used for controlling the communication and the closure of the cathode electrolytic tank, the intermediate tank and the anode electrolytic tank;
and the third three-way valve is communicated with the front of the dust removing facility and is used for controlling the entering time of the smoke/air.
2. The apparatus for membrane process water electrolysis hydrogen production in combination with carbon dioxide capture of claim 1, wherein the flue gas/air inlet is disposed at the bottom end of the cathode electrolyzer.
3. The apparatus for membrane process electrolysis hydrogen production in combination with carbon dioxide capture according to claim 1, wherein the compressor communicates with the top end of the catholyte tank through a second three-way valve.
4. The device for combined membrane process electrolysis hydrogen production and carbon dioxide capture according to claim 1, wherein the water supplementing port is arranged at the bottom side of the anode electrolytic tank, and the water supplementing port is provided with a first valve.
5. The device for combined membrane process and electrolytic hydrogen production and carbon dioxide capture as claimed in claim 1, wherein the oxygen collection port is provided at the top end of the anolyte tank, and the oxygen collection port is provided with a second valve.
6. A method for combining membrane-process electrolytic hydrogen production with carbon dioxide capture, which is characterized by using the device for combining membrane-process electrolytic hydrogen production with carbon dioxide capture according to any one of claims 1-5, and comprising the following steps:
s1, the same electrolyte solution: the cathode electrolytic tank, the intermediate tank and the anode electrolytic tank are all electrolyte solutions formed by single or compound active metal ions and strong acid roots;
s2, electrolysis: under the electrolysis action of a power supply, oxygen is generated in the anode electrolytic tank, and meanwhile, the solution becomes an acidic environment; generating hydrogen in the cathode electrolytic tank, and changing the solution into alkaline environment;
s3, carbon dioxide absorption: the flue gas is introduced into a cathode electrolytic tank after dust removal, and CO in the flue gas 2 And SO 2 Is absorbed by alkaline solution in the cathode electrolytic tank until absorption is saturated, and the smoke and CO are stopped being introduced 2 And SO 2 Formation of HCO respectively 3 - And SO 3 2- After the absorption is saturated, the method enters a step S4 for sulfur dioxide oxidation;
s4, oxidizing sulfur dioxide: air is blown into the cathode electrolytic tank, and SO is carried out by oxygen 3 2- Oxidation to SO 4 2- Dissolving in electrolyte to make SO in fume 2 Is completely absorbed;
s5, releasing carbon dioxide, namely opening a first three-way valve to enable the three groove chambers to be communicated, reacting the solution and releasing the carbon dioxide.
7. The combined membrane process and electrolytic hydrogen production and carbon dioxide capture method according to claim 6, further comprising s6. Cycle: the first three-way valve is closed, electrolysis in step S2 is started, and steps S2-S5 are circulated.
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