CN111285440A - Regeneration method of seawater acidification electrolytic cell - Google Patents
Regeneration method of seawater acidification electrolytic cell Download PDFInfo
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- CN111285440A CN111285440A CN201811488786.0A CN201811488786A CN111285440A CN 111285440 A CN111285440 A CN 111285440A CN 201811488786 A CN201811488786 A CN 201811488786A CN 111285440 A CN111285440 A CN 111285440A
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- Prior art keywords
- acidification
- seawater
- electrolytic cell
- anolyte
- ion exchange
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4611—Fluid flow
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
Abstract
The invention relates to a regeneration method of a seawater acidification electrolytic cell. The method comprises treating the acidification tank by reverse electrode regeneration, and adding Mg in the cathode plate and the ion membrane close to the cathode cavity to increase internal resistance of the device2+And Ca2+Removing ions, recovering the surface electrolytic reaction activity of the cathode plate, and simultaneously improving the free H in the ion exchange membrane+Concentration, recovery of H+The conductivity, and thus the performance of the device is restored and regenerated. The invention is characterized in that the performance of the acidification tank with increased internal resistance is recovered and regenerated by a simple and easy method under the condition of not disassembling the acidification electrolytic tank and damaging an ion exchange membrane, and the running time of the battery is prolonged.
Description
Technical Field
The invention belongs to the field of water electrolysis, and particularly relates to a regeneration method of a seawater acidification electrolytic cell.
Background
The carbon dioxide in the atmosphere is always balanced with the ocean in the whole environment, and the total concentration of the carbon dioxide in the ocean in the worldApproximately 100 mg/l. About 2-3% of the carbon dioxide is present in dissolved form and the remaining 97-98% is present in a combined state of bicarbonate and carbonate. The concentration of carbon dioxide in the sea (100mg/L) is about 140 times of the concentration in the atmosphere (0.77mg/L), so the high-concentration CO in the seawater can be efficiently utilized in an energy-saving manner2Has profound significance. Currently, the extraction of dissolved CO from seawater2The main methods of (1) are as follows: electrochemical methods, heating/pressure reduction methods, chemical precipitation methods, bubbling methods, anion exchange membrane methods, and the like. Among them, the electrochemical method has the advantages of high efficiency, low residual rate, etc. and becomes a research hotspot.
The electrochemical method is characterized in that seawater is acidified through ion exchange in an electrolysis process, carbon dioxide is prepared, hydrogen is generated at the same time, and the energy consumption in the electrochemical process accounts for most of the energy consumption of the whole seawater synthetic fuel, so that the electrochemical method is the key for the yield of the fuel oil product prepared from seawater. The electrochemical acidification device is a key component in the whole process, and plays an important role in improving the seawater acidification efficiency and reducing the energy consumption.
At present, the acidification of sea water by means of ion exchange is mentioned in patents [ US 20110281959 a1 ] and [ WO 2011142854 a1 ], using devices comprising an intermediate ion exchange module, an electrode module (divided into an anode and a cathode module) and a cation exchange membrane separating these three parts, Mg being present during the operation of the device2+And Ca2+The ion deposition causes an increase in the internal resistance of the device, which increases the power consumption in the operation of the device, resulting in a short continuous operation time of the device.
Disclosure of Invention
In particular to the cathode cavity Mg in the process of seawater acidification2+And Ca2+The ion deposition causes the electrolytic reaction of the cathode plate to be insufficient, and the ion conduction capability of the ion exchange membrane is reduced to cause the performance of the acidification electrolytic cell with increased internal resistance to recover and regenerate. The invention recovers and regenerates the performance of the acidification tank with increased internal resistance by a simple and easy method through reverse regeneration under the condition of not disassembling the acidification electrolytic tank and damaging an ion exchange membrane, and prolongs the operation time of the battery. The invention aims to provide a simple and feasible seawater acidification tank regeneration technology without disassembling acidificationUnder the conditions of an electrolytic cell and the damage of an ion exchange membrane, the performance of the acidification tank is recovered, the running time of the cell is prolonged, and the structure is simple. In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a regeneration method of a seawater acidification electrolytic tank, wherein the seawater acidification electrolytic tank is composed of an end plate, an anode part, a first ion exchange membrane, a middle ion exchange part, a second ion exchange membrane, a cathode part and an end plate which are sequentially arranged in parallel at intervals, wherein two ends of each part are respectively provided with three open pore channels, and six channels form inlet and outlet channels of catholyte, seawater and anolyte;
a flow field is arranged on the polar plate of the anode part close to the first ion exchange membrane, and a circulation channel is formed between the polar plate and the first ion exchange membrane, wherein the circulation channel is the anode part;
a flow field is arranged on the polar plate of the cathode part close to the second ion exchange membrane, and a circulation channel is formed between the polar plate and the second ion exchange membrane, wherein the circulation channel is the cathode part;
a gap serving as a seawater channel is reserved between the first ion exchange membrane and the second ion exchange membrane and is an intermediate ion exchange part;
the end plate is respectively attached to the anode part and the cathode part, and the whole device is combined into a whole through a sealing piece;
electrode liquid is introduced into the anode part and the cathode part, seawater is introduced into the intermediate ion exchange part, and the pH value of the seawater is reduced after current is loaded on the anode plate and the cathode plate;
the seawater acidification electrolytic tank also comprises an anolyte inlet, an anolyte outlet, a catholyte inlet, a catholyte outlet, a diversion electrode plate A and a diversion electrode plate B, wherein a power anode is connected with the diversion electrode plate A, a power cathode is connected with the diversion electrode plate B, during regeneration, the power anode of the seawater acidification electrolytic tank is connected with the diversion electrode plate B, the power cathode is connected with the diversion electrode plate A, catholyte is introduced into the anolyte inlet, anolyte is introduced into the catholyte inlet, and the power is turned on under the seawater acidification condition, so that the internal resistance of the device is increased in a cathode plate and an ion membrane close to a cathode cavity2+And Ca2+Removing ions and recoveringThe surface electrolytic reaction activity of the cathode plate is improved, and the free H in the ion exchange membrane is improved+Concentration, recovery of H+And (3) after the conductivity is realized, the pH value of the seawater is reduced to be less than or equal to 4, the power supply is turned off, and the deionized water is used for washing three cavities (a cathode liquid cavity, an anode liquid cavity and a seawater cavity) of the seawater acidification tank so as to remove the residual seawater and polar liquid on the surfaces of the ion exchange membrane and the polar plate, so that the performance of the acidification tank is recovered and regenerated.
Based on the technical scheme, preferably, when the acidification electrolytic cell is regenerated, the flow of the catholyte and the flow of the anolyte are doubled by using the same seawater flow and acidification operating conditions as those of the seawater acidification electrolytic cell during operation, and the pH value of the seawater is reduced to be less than or equal to 4.
Based on the technical scheme, preferably, after the pH value of the seawater is reduced to be less than or equal to 4, the power supply is cut off, before the seawater acidification electrolytic cell is washed by deionized water, the flow rate of cathode electrode liquid and the flow rate of anode electrode liquid are kept unchanged during regeneration, the electrode liquid cavity of the acidification electrolytic cell is continuously washed for 5-20 minutes to remove Mg residual on the surface2+And Ca2+Ions. And after the polar liquid cavity of the acidification tank is continuously flushed by the polar liquid, the seawater and the polar liquid cavity are flushed by deionized water. And (4) washing the seawater and the polar liquid cavity by using deionized water for 10-30 minutes.
Advantageous effects
(1) Recovering the performance of the device under the condition of not disassembling the acidification tank;
(2) can carry out continuous regeneration operation and improve the running time of the acidification tank.
Drawings
FIG. 1 is a schematic diagram of an acidification electrolyzer; wherein, 1 and 8 are end plates; 2 is a guide electrode plate A; 3 is an elastic sealing rubber thread; 4 is a first ion exchange membrane; 5 is a middle plate frame; 6 is a second ion exchange membrane; 7 is a guide electrode plate B.
Figure 2 is a block diagram of the operation of the acidification electrolyzer.
Figure 3 is a block diagram of the regeneration of the acidification electrolyzer.
Fig. 4 is a graph of pH of acidified seawater versus time.
Fig. 5 is a graph of the seawater acidification operation voltage versus time.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
In this example, the employed acidification electrolytic cell is regenerated, fig. 1 shows an electrolytic cell for seawater acidification made according to the present invention, using the acidification electrolytic cell, preparing seawater with sea salt concentration of 35g/L, pH of the prepared seawater being about 8.17, passing through the seawater acidification electrolytic cell at a flow rate of 80L/h, connecting the positive electrode of the power supply with the diversion electrode plate a, connecting the negative electrode of the power supply with the diversion electrode plate B, connecting the positive electrode with the anolyte correspondingly into the electrolytic cell, connecting the negative electrode with the catholyte correspondingly into the electrolytic cell, having a flow rate of the anolyte of 230ml/min, applying current 8A at both ends, performing seawater acidification experiments, as shown in fig. 2, seawater and anolyte enter the acidification electrolytic cell from below and flow out of the electrolytic cell from above, after the fourth seawater acidification, cutting off the power supply, passing deionized water into the seawater cavity, continuously flushing the acidification seawater cavity and the anolyte cavity at an anolyte flow rate of 230ml/min, the washing time is 10 minutes, two poles of a power supply are exchanged, the positive pole of the power supply is connected with a diversion electrode plate B, the negative pole of the power supply is connected with the diversion electrode plate A, an inlet and outlet pipeline of an acidification electrolytic cell is exchanged, catholyte is introduced into an anode liquid inlet, anolyte is introduced into a cathode liquid inlet as shown in figure 3, the seawater flow is 80L/h, the anolyte flow is 460ml/min and is introduced into the acidification electrolytic cell, the power supply is started, the seawater acidification is carried out by the same working current 8A, the pH of the seawater is reduced to 4 or below, the working relation curve of the pH of the acidified seawater and the time Before the acidification electrolytic cell is regenerated is shown in figure 4-Before, the working relation curve of the pH of the acidified seawater and the time After the acidification electrolytic cell is regenerated is shown in figure 5-Before, the working relation curve of the pH of the acidified seawater and the time is shown in figure 4-After, during the process of sea water acidification, the working voltage of the acidification electrolytic cell is gradually increased, the internal resistance is increased, the performance of the regenerated acidification electrolytic cell is recovered and regenerated, the acidification electrolytic cell can continuously operate, and the working life of the acidification electrolytic cell is prolonged.
Claims (4)
1. A regeneration method of a seawater acidification electrolytic tank comprises an anolyte inlet, an anolyte outlet, a catholyte inlet, a catholyte outlet, a diversion electrode plate A and a diversion electrode plate B, wherein a power anode is connected with the diversion electrode plate A, and a power cathode is connected with the diversion electrode plate B.
2. The method of regenerating seawater acidification electrolyzer as claimed in claim 1 wherein the flow of catholyte and anolyte are doubled while carrying out the acidification electrolyzer regeneration using the same seawater flow and operating conditions as the seawater acidification electrolyzer is operating.
3. The method for regenerating an electrolytic cell for sea water acidification according to claim 1, wherein the electrolytic cell for sea water acidification is rinsed with deionized water for 10-30 minutes.
4. The method for regenerating an electrolytic cell for acidifying seawater as defined in claim 2, wherein after the power is turned off, the anolyte chamber of the acidifying electrolytic cell is continuously washed with catholyte and anolyte for 5-20 minutes before being washed with deionized water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201811488786.0A CN111285440A (en) | 2018-12-06 | 2018-12-06 | Regeneration method of seawater acidification electrolytic cell |
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| CN201811488786.0A CN111285440A (en) | 2018-12-06 | 2018-12-06 | Regeneration method of seawater acidification electrolytic cell |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2858628Y (en) * | 2006-05-30 | 2007-01-17 | 冯庆中 | Pole-reversing operation electrochemical reactor |
| CN201175649Y (en) * | 2008-03-14 | 2009-01-07 | 北京市三元八达科技开发有限公司 | Electrodialysis desalination device of 1,3-propylene glycol fermentation liquor |
| US20130206605A1 (en) * | 2010-05-11 | 2013-08-15 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Extraction of carbon dioxide and hydrogen from seawater and hydrocarbon production therefrom |
| CN103603005A (en) * | 2013-11-12 | 2014-02-26 | 广州赛爱环境保护技术开发有限公司 | Continuous weakly alkaline high-concentration hydrogen-rich water electrolysis device |
-
2018
- 2018-12-06 CN CN201811488786.0A patent/CN111285440A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2858628Y (en) * | 2006-05-30 | 2007-01-17 | 冯庆中 | Pole-reversing operation electrochemical reactor |
| CN201175649Y (en) * | 2008-03-14 | 2009-01-07 | 北京市三元八达科技开发有限公司 | Electrodialysis desalination device of 1,3-propylene glycol fermentation liquor |
| US20130206605A1 (en) * | 2010-05-11 | 2013-08-15 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Extraction of carbon dioxide and hydrogen from seawater and hydrocarbon production therefrom |
| CN103603005A (en) * | 2013-11-12 | 2014-02-26 | 广州赛爱环境保护技术开发有限公司 | Continuous weakly alkaline high-concentration hydrogen-rich water electrolysis device |
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