CN111635058A - Concentration and reduction device and process for desulfurization wastewater of power plant - Google Patents
Concentration and reduction device and process for desulfurization wastewater of power plant Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- 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
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention relates to a concentration and reduction device and a concentration and reduction process for desulfurization wastewater of a power plant, wherein the device comprises a triple box, an ultrafiltration device and an electrolysis device, the triple box is provided with a dosing device and an inlet for desulfurization wastewater of the power plant to flow into, the ultrafiltration device is connected with the triple box, and the electrolysis device is connected with the ultrafiltration device; the process is characterized in that desulfurization wastewater generated by a power plant flows into a triple box through an inlet of the triple box provided with a dosing device, flows into an ultrafiltration device through a desulfurization wastewater outlet of the triple box after sedimentation and flocculation of the triple box, and is filtered again through the ultrafiltration device; the desulfurization waste water flows into the electrolysis device from the desulfurization waste water outlet of the ultrafiltration device, and after the desulfurization waste water is electrolyzed, oxygen and chlorine are generated in the anode chamber of the electrolysis device, and hydrogen is generated in the cathode chamber of the electrolysis device. The invention mainly utilizes the electrolysis technology to concentrate and reduce the amount of the wastewater, and simultaneously generates byproducts which can be recycled, and the whole process is green and environment-friendly, clean and efficient, has lower cost and is easy to popularize.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, relates to a device and a process for concentrating and reducing desulfurization wastewater of a power plant and simultaneously generating byproduct gas, and particularly relates to a process for concentrating and reducing wastewater by utilizing an electrolysis technology.
Background
Limestone-gypsum wet desulphurization is the most widely used flue gas desulphurization technology in domestic and foreign power plants, and has the advantages of higher desulphurization efficiency and good gypsum quality. However, this method has a disadvantage in that a certain amount of high-concentration waste water is periodically discharged to the outside. Because desulfurization waste water is the waste water of power plant's tail end, it has following characteristics: (1) the pollution components in the wastewater are influenced by factors such as the water quality, the coal type, the discharge period and the like of the desulfurization process, and different power plants have great difference; (2) the desulfurization wastewater is discharged intermittently at regular intervals, and the water quantity fluctuation is large; (3) ca in wastewater2+、Mg2+、Cl-、SO42-And soluble solids contentVery high, these high concentrations of ions can have some detrimental effect on subsequent processing systems. Therefore, in order to realize zero emission of wastewater from the whole plant, the wastewater must be subjected to reduction concentration and then to further treatment.
At present, most domestic coal-fired power plants adopt a membrane method and a thermal method concentration and decrement process. The membrane concentration process comprises nanofiltration, reverse osmosis, electrodialysis, forward osmosis, membrane distillation and the like. But because desulfurization waste water contains a large amount of salt to the corrosion and the pollution of rete can be caused when desulfurization waste water is concentrated to conventional membrane treatment mode, seriously reduced membrane treatment device to desulfurization waste water's concentration effect and stability, the producer also need regularly change the rete, increased corresponding concentration process cost. Thermal concentration is a traditional chemical process, and comprises steam heating evaporation, flue gas evaporation, natural evaporation, humidification and dehumidification and the like. However, due to the high investment cost of the thermal method, the selection of the thermal method concentration process needs to be fully demonstrated technically and economically.
For example utility model patent (CN 209974506U) discloses a concentrated decrement system of wet flue gas desulfurization waste water, mainly includes dust remover, flue, draught fan, desulfurizing tower, three headers, depositing reservoir, concentrated pond and waste water delivery pump. The system utilizes the high-temperature raw flue gas after dust removal to evaporate part of the desulfurization wastewater, thereby realizing concentration and decrement. But this system has carried out transformation to former flue, and the civil engineering cost is higher, is unfavorable for the power plant to make profit.
For another example, the invention patent (CN 108793522 a) discloses a concentration and reduction process for desulfurization wastewater, which mainly uses nanofiltration, electrodialysis and high-pressure reverse osmosis to concentrate wastewater. Because the salt content of the desulfurization wastewater is higher, membrane fouling is easily caused when the desulfurization wastewater is concentrated by a membrane treatment mode, and the maintenance cost and the operation cost are higher.
From the above, the existing concentration treatment method for desulfurization wastewater of power plants still has the problems of high treatment cost and complex process. Therefore, the development of a desulfurization wastewater concentration and reduction process which can be adapted to the sustainable development and low-carbon environmental protection concept in the current era is urgently needed.
On the other hand, hydrogen energy has the characteristics of cleanness, high efficiency, reproducibility, high energy density and the like, and is considered to be one of the most potential energy sources in the future. In recent years, the value of hydrogen energy has become increasingly prominent in the current society due to unstable supply of oil and gas resources and high requirements of human beings on sustainable development. The hydrogen has rich sources, can be produced by using fossil energy such as coal, petroleum and the like, and can also be produced by using electrolyzed water. Wherein, the raw material for hydrogen production by water electrolysis is water, and only a small amount of alkali liquor wastewater is generated in the production process, thus being a relatively green and environment-friendly hydrogen production technology.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a device and a process for concentrating and reducing power plant wastewater, which can couple hydrogen production by electrolyzed water and concentration and reduction of desulfurization wastewater.
The technical means adopted by the invention are as follows.
The invention provides a concentration and reduction device for desulfurization wastewater of a power plant, which comprises: the three-way box is provided with a dosing device and an inlet for desulfurization wastewater of a power plant to flow in; the ultrafiltration device is connected to the desulfurization wastewater outlet of the triple box; and the electrolysis device is connected to the desulfurization wastewater outlet of the ultrafiltration device.
The device also comprises an adsorption separation device which is connected with a gas outlet of the anode chamber of the electrolysis device.
The device also comprises an evaporative crystallization device, wherein the evaporative crystallization device is connected to the desulfurization waste water outlet of the electrolysis device.
Wherein, the fresh water outlet of the evaporative crystallization device is connected with the ultrafiltration device and/or the drug adding device.
The invention also provides a concentration and decrement process of the desulfurization wastewater of the power plant, which comprises the following steps: desulfurization wastewater generated by a power plant flows into the triple box through an inlet of the triple box provided with a dosing device, flows into the ultrafiltration device through a desulfurization wastewater outlet of the triple box after sedimentation and flocculation of the triple box, and is filtered again by the ultrafiltration device; and the desulfurized wastewater flows into an electrolysis device from a desulfurized wastewater outlet of the ultrafiltration device, and after the desulfurized wastewater is electrolyzed, oxygen and chlorine are generated in an anode chamber of the electrolysis device, and hydrogen is generated in a cathode chamber of the electrolysis device.
And the oxygen and the chlorine generated in the anode chamber are separated in an adsorption separation device to obtain the separated oxygen and chlorine.
Wherein the total dissolved solid content of the original power plant desulfurization wastewater is 10000-60000mg/L, wherein Ag+、Hg+、Fe3 +、Cu2+The total content of (A) is less than 100 mg/L.
And when the content of suspended matters in the desulfurization wastewater filtered by the ultrafiltration device is less than or equal to 0.2mg/L, discharging the desulfurization wastewater into the electrolysis device.
Wherein, when the total dissolved solid content of the desulfurization wastewater electrolyzed by the electrolysis device is increased to 300000-400000mg/L, the desulfurization wastewater is discharged into the evaporative crystallization device from the desulfurization wastewater outlet of the electrolysis device, and the desulfurization wastewater is evaporated and crystallized to obtain industrial salt and fresh water.
And fresh water generated by the evaporative crystallization device flows into the ultrafiltration device and/or the medicine adding device for secondary utilization.
The advantageous effects produced by the present invention are as follows.
(1) The high salinity in the desulfurization waste water has mainly been utilized, and then its electric conductivity is high, is favorable to carrying out the electrolysis and reaches concentrated decrement purpose, has solved the problem that the power plant waste water is difficult to handle with electrolysis water hydrogen manufacturing and desulfurization waste water concentrated decrement coupling.
(2) The invention generates hydrogen, oxygen, chlorine and industrial salt products which can be recycled for the second time while concentrating and reducing the desulfurization wastewater, thereby achieving the purposes of saving energy, reducing emission and increasing the income of a power plant.
(3) Compared with the prior art, the device and the process for concentrating and reducing the desulfurization wastewater of the power plant mainly adopt an electrolysis mode to concentrate and reduce the wastewater, hardly consume any chemical agent, and have the advantages of low cost, environmental protection, cleanness, high efficiency and easy popularization.
Drawings
FIG. 1 is a schematic structural diagram of an embodiment of a concentration and reduction device for desulfurization wastewater of a power plant.
Detailed Description
Fig. 1 is a schematic structural diagram of an embodiment of a concentration and reduction device for desulfurization wastewater of a power plant according to the present invention. The concentrated decrement device of power plant's desulfurization waste water mainly contains three header 1, ultrafiltration device 3 and electrolytic device 4, and wherein three header 1 is equipped with the entry that charge device 2 and power plant's desulfurization waste water flowed into, and ultrafiltration device 3 is connected in three header 1's desulfurization waste water export, and electrolytic device 4 is connected in ultrafiltration device 3's desulfurization waste water export.
Wherein, the triple box 1 mainly has the functions of sedimentation and flocculation to remove suspended matters in the wastewater; the medicine adding device 2 is used for adding a coagulant, a coagulant aid, acid or alkali and the like into the triple box 1; the ultrafiltration device 3 functions to further purify impurities in the wastewater, which hardly changes the ion concentration in the wastewater; the electrolysis unit 4 electrolyzes water in the desulfurization wastewater to produce hydrogen, oxygen and chlorine, thereby realizing the purpose of wastewater concentration and reduction, and the electrolysis bath adopted by the electrolysis unit can be: an alkaline water electrolytic cell, a proton exchange membrane water electrolytic cell and a solid oxide water electrolytic cell, preferably an alkaline water electrolytic cell.
As shown in the figure, in order to further perform secondary utilization on the electrolyzed desulfurization wastewater and other products, the concentration and reduction device for desulfurization wastewater in power plant of the embodiment is further provided with an evaporative crystallization device 5 and an adsorption separation device 6. Wherein, the evaporative crystallization device 5 is connected with the desulfurization waste water outlet of the electrolysis device 4 and is used for further evaporating and crystallizing the desulfurization waste water to generate available industrial salt and fresh water; the adsorption separation device 6 is connected to a gas outlet of the anode chamber 41 of the electrolysis device 4 for separating chlorine gas and oxygen gas generated in the anode chamber.
Wherein the adsorbing material of the adsorption separation device 6 can be activated carbon or molecular sieve, preferably activated carbon; the adsorption mode can be pressure swing adsorption or temperature swing adsorption, and is preferably pressure swing adsorption.
Meanwhile, the fresh water outlet of the evaporative crystallization device 5 in this embodiment can be connected to the ultrafiltration device 3 and the dosing device 2 of the triple box 1, so that the fresh water generated after crystallization can be used for supplementing the water in the ultrafiltration device 3 and the dosing device 2.
In addition, three types of byproduct gases generated by the electrolysis device 4 can be recycled in a mode of additionally arranging a hydrogen collecting and storing device, a chlorine collecting and storing device, an oxygen collecting and storing device and the like, so that the purposes of saving energy or increasing the income of a power plant are achieved.
The concentration and decrement process of the desulfurization wastewater of the power plant based on the device of the embodiment shown in FIG. 1 comprises the following steps: the desulfurization wastewater of the power plant firstly passes through a triple box 1 provided with a dosing device 2, and suspended matters in the wastewater are removed through the sedimentation and flocculation of the triple box 1; then the wastewater flows into the ultrafiltration device 3 through the desulfurization wastewater outlet of the triple box 1 to further purify impurities in the wastewater, then the wastewater flows into the electrolysis device 4 through the desulfurization wastewater outlet of the ultrafiltration device 3, chlorine and oxygen are generated in the anode chamber 41 of the electrolysis device 4 through electrolysis, hydrogen capable of being recycled is generated in the cathode chamber 42, and the chlorine and the oxygen generated in the anode chamber 41 can be separated through the adsorption separation device 6 and then recycled; the desulfurization waste water electrolyzed by the electrolysis device 4 can flow into the evaporative crystallization device 5 again, industrial salt and fresh water are generated after evaporative crystallization, and the fresh water can be used for supplementing water in the ultrafiltration device 3 and/or the dosing device 2.
Wherein, the original power plant desulfurization wastewater is generally acidic, and the pH value is between 4 and 6, for example, 4, 5, 6, and the like, and preferably 4; the total dissolved solids content of the original desulfurization waste water is 10000-60000mg/L, which can be 10000mg/L, 20000mg/L, 30000mg/L and 60000mg/L, preferably 60000 mg/L.
In addition, if heavy metal ions exist in the wastewater, heavy metal oxides are generated at the anode, but because the desulfurization wastewater is generally acidic as described above, the heavy metal oxides are decomposed by the acid after the electrolysis is finished, i.e., the influence of the heavy metal ions on the electrolysis process can be eliminatedAnd (4) removing. Therefore, the desulfurization waste water may contain a small amount of Ag+、Hg+、Fe3+、Cu2+Preferably, Ag in the wastewater+、Hg+、Fe3+、Cu2+The total content of (A) is less than 100 mg/L.
When the content of suspended matters in the desulfurization waste water filtered by the ultrafiltration device 3 is 0.2mg/L or less, for example, 0.2mg/L, 0.1mg/L, 0.05mg/L, 0.02mg/L, and preferably 0.2mg/L, the desulfurization waste water is discharged to the electrolysis device 4 to be electrolyzed.
When the total dissolved solid content of the desulfurization waste water electrolyzed by the electrolysis device 4 is increased to 300000-400000mg/L, it may be, for example, 310000mg/L, 320000mg/L, 400000mg/L, etc., preferably 400000mg/L, and then discharged to the evaporative crystallization device 5 through the desulfurization waste water outlet of the electrolysis device 4.
The waste water concentration and reduction device and the process can also be suitable for concentration and reduction of other types of power plant waste water, such as: circulating sewage or reverse osmosis concentrated water.
Claims (10)
1. The utility model provides a concentrated decrement device of desulfurization waste water of power plant which characterized in that contains:
the device comprises a triple box (1), wherein the triple box (1) is provided with a dosing device (2) and an inlet for desulfurization wastewater of a power plant to flow into;
the ultrafiltration device (3), the ultrafiltration device (3) is connected to the desulfurization wastewater outlet of the triple box (1);
the electrolysis device (4), the electrolysis device (4) is connected with the desulfurization waste water outlet of the ultrafiltration device (3).
2. The power plant desulfurization wastewater concentration and reduction device according to claim 1, further comprising an adsorption separation device (6), wherein the adsorption separation device (6) is connected to a gas outlet of the anode chamber (41) of the electrolysis device (4).
3. The power plant desulfurization waste water concentration and reduction device according to claim 1 or 2, further comprising an evaporative crystallization device (5), wherein the evaporative crystallization device (5) is connected to the desulfurization waste water outlet of the electrolysis device (4).
4. The power plant desulfurization wastewater concentration and reduction device according to claim 3, wherein the fresh water outlet of the evaporative crystallization device (5) is connected to the ultrafiltration device (3) and/or the chemical adding device (2).
5. The concentration and decrement process of the desulfurization wastewater of the power plant is characterized in that the desulfurization wastewater generated by the power plant flows into a triple box (1) through an inlet of the triple box (1) provided with a dosing device (2), flows into an ultrafiltration device (3) through a desulfurization wastewater outlet of the triple box (1) after the sedimentation and flocculation of the triple box (1), and is filtered again through the ultrafiltration device (3); the desulfurization wastewater flows into an electrolysis device (4) from a desulfurization wastewater outlet of the ultrafiltration device (3), after the desulfurization wastewater is electrolyzed, oxygen and chlorine are generated in an anode chamber (41) of the electrolysis device (4), and hydrogen is generated in a cathode chamber (42) of the electrolysis device (4).
6. The concentration and reduction process for desulfurization waste water of power plant according to claim 5, wherein oxygen and chlorine generated in the anode chamber (41) are separated in the adsorption separation device (6) to obtain separated oxygen and chlorine.
7. The concentration and decrement process for desulfurization waste water from power plant as claimed in claim 5, wherein the total dissolved solids content of the original desulfurization waste water from power plant is 10000-60000mg/L, in which Ag is+、Hg+、Fe3+、Cu2+The total content of (A) is less than 100 mg/L.
8. The concentration and reduction process for desulfurization waste water from power plants in accordance with claim 7, wherein the desulfurization waste water filtered by the ultrafiltration device (3) is discharged to the electrolysis device (4) when the content of suspended substances in the desulfurization waste water is less than or equal to 0.2 mg/L.
9. The concentration and decrement process for desulfurization waste water of power plant according to any one of claims 5 to 8, characterized in that, when the total dissolved solid content of the desulfurization waste water electrolyzed by the electrolysis device (4) is increased to 300000-400000mg/L, the desulfurization waste water is discharged from the desulfurization waste water outlet of the electrolysis device (4) to the evaporation crystallization device (5), and the desulfurization waste water is evaporated and crystallized to obtain industrial salt and fresh water.
10. The concentration and reduction process for desulfurization waste water of power plant according to claim 9, characterized in that the fresh water generated by the evaporative crystallization device (5) flows into the ultrafiltration device (3) and/or the chemical adding device (2) for secondary utilization.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024037041A1 (en) * | 2022-08-19 | 2024-02-22 | 国家能源集团新能源技术研究院有限公司 | Desulfurization wastewater treatment system and method |
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| WO2024037041A1 (en) * | 2022-08-19 | 2024-02-22 | 国家能源集团新能源技术研究院有限公司 | Desulfurization wastewater treatment system and method |
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