CN117228898A - Method for treating desulfurization wastewater of thermal power plant by mono/divalent anion high-selectivity displacement electrodialysis - Google Patents
Method for treating desulfurization wastewater of thermal power plant by mono/divalent anion high-selectivity displacement electrodialysis Download PDFInfo
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Abstract
The invention discloses a method for treating desulfurization wastewater of a thermal power plant by using high-selectivity displacement electrodialysis of mono-and divalent anions, which combines flocculation sedimentation pretreatment, ultrafiltration membrane system treatment and a combined process of selective displacement electrodialysis of mono-and divalent anions and evaporative crystallization to treat the desulfurization wastewater of the thermal power plant. The process realizes zero emission of desulfurization wastewater, saves water resources, achieves the aim of recycling comprehensive utilization, has simple process and is suitable for industrialized popularization and application.
Description
Technical Field
The invention belongs to the field of chemical wastewater treatment, and particularly relates to a process method for treating desulfurization wastewater of a thermal power plant by high-selectivity electrodialysis replacement of mono-and divalent anions.
Background
The desulfurization wastewater of the power plant is the discharge water of an absorption tower in the wet desulfurization (limestone/gypsum method) process of boiler flue gas. When the process is operated, HCl discharged by flue gas and Cl in process water - A large amount of sulfides and heavy metals in the coal can enter the slurry in the desulfurization absorption tower, the slurry is continuously recycled, and in the process, the soluble salt of the slurry is continuously concentrated, wherein Cl is contained in the slurry - The increased content of (c) will increase the corrosiveness of the slurry and also affect the quality of the gypsum and the solubility of the limestone, thereby reducing the desulfurization efficiency. Therefore, in order to maintain the stable performance of the system, fresh slurry needs to be continuously replenished, and waste water is discharged from the desulfurization system in time, so that the material balance in the whole desulfurization system is ensured. Thus the discharged wastewater contains a large amount of Cl - Heavy metal plasma.
The amount and quality of the desulfurization waste water are unstable, wherein the quality of the desulfurization waste water can be different along with the different types of the fire coal attribute, the desulfurization device and the unit capacity used by the thermal power plant, and even the desulfurization device which is identical is not identical in the different discharge stages. Although the desulfurization waste water is discharged in a smaller amount, the desulfurization waste water is discharged after being strictly treated, otherwise, the desulfurization waste water can pollute the surrounding environment. At present, the conventional treatment modes of chloride ions in desulfurization wastewater mainly comprise a chemical precipitation method, an ash removal system for discharging the desulfurization wastewater, an evaporation concentration method and a membrane separation technology.
The chemical precipitation method requires adding a large amount of chemical agent, has high treatment cost, generates a large amount of sludge, and has poor effect on chloride ion removal. In actual operation of a system such as spray evaporation and the like, system equipment is easy to corrode, and safety production of the equipment is affected. The nanofiltration membrane and the reverse osmosis membrane of the membrane separation method are easy to be fouled and blocked by calcium and magnesium ions in the desulfurization wastewater, and the cleaning frequency is high.
Therefore, the proper treatment method is adopted to recycle the desulfurization wastewater, so that zero emission is realized, the overall stability of limestone-gypsum wet desulfurization system equipment is improved, and the difficulty is high.
Disclosure of Invention
Based on the problems existing in the prior art, the invention aims to provide a method for treating desulfurization wastewater of a thermal power plant by high-selectivity substitution electrodialysis of mono/divalent anions, so as to solve the recycling problem of desulfurization wastewater in the existing limestone-gypsum wet desulfurization system and realize zero emission of desulfurization wastewater.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for treating desulfurization wastewater of a thermal power plant by high-selectivity substitution electrodialysis of mono-and divalent anions comprises the following steps:
step 1, pretreatment of desulfurization wastewater
Pretreating the desulfurization wastewater to be treated, and removing suspended matter impurities and heavy metal ions in the desulfurization wastewater by adding medicines for flocculation precipitation.
Step 2, ultrafiltration membrane filtration treatment
The pretreated desulfurization wastewater directly enters an ultrafiltration membrane system for treatment, and macromolecular substances, colloid substances and suspended matters which are not completely removed in the water are intercepted, so that the SS (suspended solids) of the treated desulfurization wastewater is less than 5mg/L.
Step 3, high-selectivity electrodialysis replacement treatment of mono/dianions
Setting a mono-di-anion high-selectivity substitution electrodialysis treatment system, wherein the treatment system comprises a mono-di-anion high-selectivity substitution electrodialysis membrane assembly and a direct current power supply; the mono-and divalent anion high-selectivity replacement electrodialysis membrane assembly is composed of a first cation exchange membrane, a mono-and divalent high-selectivity anion exchange membrane, a second cation exchange membrane and an anion exchange membrane which are sequentially and alternately overlapped and then added with a runner separation net and a sealing gasket; an anode plate and a cathode plate are fixed on two sides of the electrodialysis replacement membrane assembly, and the anode plate is connected with the anode of a power supply, and the cathode plate is connected with the cathode of the power supply; an anode chamber is formed between the anode plate and the adjacent cation exchange membrane, and a cathode chamber is formed between the cathode plate and the adjacent cation exchange membrane; a sodium chloride 1 compartment is formed between the first cation exchange membrane and the mono/bivalent high selectivity anion exchange membrane, a desulfurization wastewater 2 compartment is formed between the mono/bivalent high selectivity anion exchange membrane and the second cation exchange membrane, a concentration 3 compartment is formed between the second cation exchange membrane and the anion exchange membrane, and a sodium chloride 4 compartment is formed between the anion exchange membrane and the first cation exchange membrane at the other side; forming a plurality of repeating units of "sodium chloride 1 compartment-desulfurization wastewater 2 compartment-concentration 3 compartment-sodium chloride 4 compartment" between the anode compartment and the cathode compartment;
after passing through a cartridge filter, the desulfurization wastewater filtered by an ultrafiltration membrane enters a desulfurization wastewater 2 compartment of a mono/divalent anion high-selectivity replacement electrodialysis treatment system, sodium chloride solution is introduced into a sodium chloride 1 compartment and a sodium chloride 4 compartment of replacement electrodialysis, pure water is introduced into a concentration 3 compartment, and replacement electrodialysis treatment is carried out, so that chloride ions and cations in the desulfurization wastewater are enriched in the concentration 3 compartment, and high-concentration chloride salt is obtained;
after the electrodialysis treatment is replaced, the desulfurization wastewater in the desulfurization wastewater 2 compartment is returned to the limestone-gypsum wet desulfurization system for recycling;
after the electrodialysis replacement treatment, the high-concentration chloride salt solution in the concentrated 3 compartments enters the next working procedure for treatment.
Step 4, further treatment of the concentrating chamber liquid
The feed liquid in the concentrating 3 compartments is output to an evaporation crystallization system through a pipeline for evaporation to obtain solid salt, and the liquid obtained by evaporation is returned to the concentrating 3 compartments, so that the water circulation in the whole limestone-gypsum wet desulfurization system is realized.
Further, in the step 1, the agents for the medicated flocculation sedimentation are PAM and PAC.
In step 2, the ultrafiltration membrane in the ultrafiltration membrane system is a hollow fiber ultrafiltration membrane, and a pore size filtration mode driven by a lower transmembrane pressure is adopted.
Further, in step 3, the mono/dianion high selectivity electrodialysis replacement system further comprises a feed solution storage tank. The feed liquid storage tank comprises an electrode chamber storage tank, a sodium chloride storage tank, a desulfurization waste water storage tank and a concentrating chamber storage tank; the anode chamber and the cathode chamber are connected in series through a pipeline and are communicated with an electrode chamber storage tank; the inlet and the outlet of the desulfurization waste water 2 compartment are communicated with the desulfurization waste water storage tank through pipelines, the inlet and the outlet of the sodium chloride 1 compartment and the sodium chloride 4 compartment are respectively communicated with the sodium chloride storage tank in parallel through pipelines, and the inlet and the outlet of the concentration 3 compartment are respectively communicated with the concentration chamber storage tank through pipelines.
Further, the mono/divalent highly selective anion exchange membrane is an anion exchange membrane that is permeable only to monovalent anions and blocks permeation of multivalent anions.
Further, the mono/divalent anion high selectivity displacement electrodialysis treatment system is also provided with a circulating pump between each compartment and the corresponding feed liquid storage tank; the flow of the circulating pumps of the sodium chloride 1 compartment, the desulfurization wastewater 2 compartment, the concentration 3 compartment and the sodium chloride 4 compartment are matched with each other to replace the electrodialysis membrane assembly, so that the flow rate of the membrane surface is not lower than 3cm/s.
Further, in step 4, the evaporative crystallization system is a forced circulation evaporative crystallizer, an MVR evaporative crystallizer or a multi-effect evaporative crystallization device.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention utilizes pretreatment, ultrafiltration membrane, mono/divalent anion high-selectivity replacement electrodialysis and evaporative crystallization technology to treat the desulfurization wastewater of the thermal power plant, can realize the recycling of the desulfurization wastewater, saves water resources, achieves the aim of recycling comprehensive utilization, and reduces the waste of water resources and environmental pollution.
2. The method has simple process and low energy consumption, is suitable for desulfurization wastewater with different water quality conditions, and is suitable for industrialized popularization and application.
Drawings
FIG. 1 is a process flow diagram of the invention for treating desulfurization wastewater of a thermal power plant by mono/divalent anion high-selectivity displacement electrodialysis;
FIG. 2 is a membrane layout diagram of a mono/dianion high selectivity replacement electrodialysis membrane assembly of the invention.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
The mono/dianion high selectivity replacement electrodialysis treatment system used in the examples described below comprises a mono/dianion high selectivity replacement electrodialysis membrane module and a dc power supply. As shown in figure 2, the mono-and divalent anion high-selectivity replacement electrodialysis membrane assembly is formed by sequentially and alternately superposing a first cation exchange membrane, a mono-and divalent anion exchange membrane, a second cation exchange membrane and an anion exchange membrane and then adding a flow passage separation net and a sealing gasket. An anode plate and a cathode plate are fixed on two sides of the electrodialysis replacement membrane assembly, and the anode plate is connected with the anode of a power supply, and the cathode plate is connected with the cathode of the power supply; the anode plate and the cathode plate are both close to the cation exchange membrane. An anode chamber is formed between the anode plate and the adjacent cation exchange membrane, and a cathode chamber is formed between the cathode plate and the adjacent cation exchange membrane; a sodium chloride 1 compartment is formed between the first cation exchange membrane and the mono/bivalent high selectivity anion exchange membrane, a desulfurization wastewater 2 compartment is formed between the mono/bivalent high selectivity anion exchange membrane and the second cation exchange membrane, a concentration 3 compartment is formed between the second cation exchange membrane and the anion exchange membrane, and a sodium chloride 4 compartment is formed between the anion exchange membrane and the first cation exchange membrane at the other side. Specifically, in the following examples, the first cation exchange membrane, mono/divalent anion exchange membrane with high selectivity, the second cation exchange membrane, and the anion exchange membrane were SYMC-2, SYMIA-3, SYMC-2, and SYMA-2, respectively, manufactured by Shen cation Membrane Co., midage, anhui were used.
Example 1
A process method for treating desulfurization wastewater of a thermal power plant by high-selectivity substitution electrodialysis of mono-and divalent anions comprises the following steps:
step 1, desulfurization wastewater (pH=6-7) enters a pretreatment system through a raw water pump to be pretreated, the pretreatment system adopts dosing flocculation precipitation, the added medicament is PAM and PAC, the dosage of the PAM is 10 g/ton of water, the dosage of the PAC is 20 g/ton of water, and suspended matter impurities and heavy metal ions in the desulfurization wastewater are removed.
And 2, directly introducing the pretreated desulfurization wastewater into an ultrafiltration membrane system for treatment, and intercepting macromolecular substances, colloid substances and suspended matters which are not completely removed in the water, so that the SS (suspended solids) of the treated desulfurization wastewater is less than 5mg/L.
Step 3, after the desulfurization wastewater filtered by the ultrafiltration membrane system passes through a cartridge filter, directly conveying the desulfurization wastewater to a desulfurization wastewater storage tank of a mono/divalent anion high-selectivity electrodialysis replacement device, simultaneously introducing 3wt% of sodium chloride solution into a sodium chloride 1 compartment and a sodium chloride 4 compartment of electrodialysis replacement, concentrating the 3 compartment, introducing pure water, and adding 3wt% of sodium sulfate solution into an electrode chamber storage tank. Starting the circulating pumps of all chambers, and setting the flow to be 3m 3 And/h. Turning on a direct current power supply to perform electrodialysis replacement treatment on desulfurization wastewater; stopping when the mass concentration of chloride ions in the feed liquid in the desulfurization wastewater 2 compartment is lower than 5 g/L. The feed liquid in the desulfurization waste water storage tank is output through a pipeline and returned to the limestone-desulfurization waste water system for recycling, the feed liquid in the concentrating 3 compartment enters the evaporation crystallization tank for further concentration, and the solution in the sodium chloride storage tank is continuously circulated.
And step 3, starting an evaporation crystallization system, evaporating and concentrating the concentrated solution to obtain solid crystals, and returning the evaporated liquid to a storage tank of the electrodialysis replacement concentration chamber to continue concentration circulation.
The present example examined the concentration of chloride ions in the influent water of desulfurization wastewater, the concentration of chloride ions after treatment of desulfurization wastewater, and the removal rate of chloride ions at different electrodialysis voltage substitutions at a certain circulation flow rate, and the results are shown in table 1.
TABLE 1 concentration of chloride ions in influent water of desulfurization wastewater, concentration of chloride ions after treatment of desulfurization wastewater, and removal rate of chloride ions for desulfurization wastewater at different operating voltages
From the above, in this embodiment, the chemical adding pre-precipitation system, the ultrafiltration system, the mono/divalent anion high-selectivity replacement electrodialysis device and the evaporation crystallization system are used for treating desulfurization wastewater with the salt content of 3wt%, so that chloride ions in the desulfurization wastewater of the wet thermal power plant can be effectively removed, the chloride ion removal rate in the desulfurization wastewater reaches over 73%, the recycling of the desulfurization wastewater can be realized, water resources are saved, the corrosion of desulfurization slurry to a desulfurization tower is greatly reduced, the experimental life is prolonged, and the method is suitable for industrial popularization and application.
Example 2
A process method for treating desulfurization wastewater of a thermal power plant by high-selectivity substitution electrodialysis of mono-and divalent anions comprises the following steps:
step 1, desulfurization wastewater (pH=6-7) enters a pretreatment system through a raw water pump to be pretreated, wherein the pretreatment system is dosing and precipitation, the added medicament is PAM and PAC, the PAM dosage is 12 g/ton of water, the PAC dosage is 20 g/ton of water, and suspended matter impurities and heavy metal ions in the desulfurization wastewater are removed.
And 2, directly introducing the pretreated desulfurization wastewater into an ultrafiltration membrane system for treatment, and intercepting macromolecular substances, colloid substances and suspended matters which are not completely removed in the water. The SS of the treated desulfurization wastewater is enabled to be less than 5mg/L.
Step 3, after the desulfurization wastewater filtered by the ultrafiltration membrane system passes through a cartridge filter, directly conveying the desulfurization wastewater to a desulfurization wastewater storage tank of a mono/divalent anion high-selectivity replacement electrodialysis device, simultaneously introducing 4wt% sodium chloride solution into a sodium chloride 1 compartment and a sodium chloride 4 compartment of replacement electrodialysis, concentrating the 3 compartment, introducing pure water, and adding 3wt% sodium chloride solution into an electrode chamber storage tank. Starting the circulating pumps of all chambers, and setting the flow to be 3m 3 And/h. Turning on a direct current power supply to perform electrodialysis replacement treatment on desulfurization wastewater; stopping when the mass concentration of chloride ions in the feed liquid in the desulfurization wastewater 2 compartment is lower than 5 g/L. The feed liquid in the desulfurization waste water storage tank is output through a pipeline and returned to the limestone-desulfurization waste water system for recycling, the feed liquid in the concentrating 3-compartment enters the evaporation crystallization tank for further concentration, and the solution in the sodium chloride circulation tank is continuously circulated.
And step 3, starting an evaporation crystallization system, evaporating and concentrating the concentrated solution to obtain solid crystals, and returning the evaporated liquid to a storage tank of the electrodialysis replacement concentration chamber to continue concentration circulation.
The present example examined the concentration of chloride ions in the influent water of desulfurization wastewater, the concentration of chloride ions after treatment of desulfurization wastewater, and the removal rate of chloride ions at different electrodialysis voltage substitutions at a certain circulation flow rate, and the results are shown in table 2.
TABLE 2 concentration of chloride ions in influent water, concentration of chloride ions after treatment of desulfurization wastewater, and removal rate of chloride ions for desulfurization wastewater at different operating voltages
From the above, in this embodiment, the chemical adding pre-precipitation system, the ultrafiltration system, the mono/divalent anion high-selectivity replacement electrodialysis device and the evaporation crystallization system are used for treating desulfurization wastewater with the salt content of 4wt%, so that chloride ions in the desulfurization wastewater of the wet thermal power plant can be effectively removed, the chloride ion removal rate in the desulfurization wastewater reaches over 79%, the recycling of the desulfurization wastewater can be realized, water resources are saved, the corrosion of desulfurization slurry to a desulfurization tower is greatly reduced, the experimental life is prolonged, and the method is suitable for industrial popularization and application.
The above description of the specific embodiments of the present invention has been given by way of example only, and the present invention is not limited to the above described specific embodiments. Any equivalent modifications and substitutions for the present invention will occur to those skilled in the art, and are also within the scope of the present invention. Accordingly, equivalent changes and modifications are intended to be included within the scope of the present invention without departing from the spirit and scope thereof.
Claims (7)
1. A method for treating desulfurization wastewater of a thermal power plant by high-selectivity substitution electrodialysis of mono-and divalent anions, which is characterized by comprising the following steps:
step 1, pretreatment of desulfurization wastewater
Removing suspended matter impurities and heavy metal ions in the desulfurization wastewater to be treated through adding medicines and flocculating settling;
step 2, ultrafiltration membrane filtration treatment
Directly introducing the pretreated desulfurization wastewater into an ultrafiltration membrane system for treatment, and intercepting macromolecular substances, colloid substances and suspended matters which are not completely removed in the water, so that the SS (suspended solids) of the treated desulfurization wastewater is less than 5mg/L;
step 3, high-selectivity electrodialysis replacement treatment of mono/dianions
Setting a mono-di-anion high-selectivity substitution electrodialysis treatment system, wherein the treatment system comprises a mono-di-anion high-selectivity substitution electrodialysis membrane assembly and a direct current power supply; the mono-and divalent anion high-selectivity replacement electrodialysis membrane assembly is composed of a first cation exchange membrane, a mono-and divalent high-selectivity anion exchange membrane, a second cation exchange membrane and an anion exchange membrane which are sequentially and alternately overlapped and then added with a runner separation net and a sealing gasket; an anode plate and a cathode plate are fixed on two sides of the electrodialysis replacement membrane assembly, and the anode plate is connected with the anode of a power supply, and the cathode plate is connected with the cathode of the power supply; an anode chamber is formed between the anode plate and the adjacent cation exchange membrane, and a cathode chamber is formed between the cathode plate and the adjacent cation exchange membrane; a sodium chloride 1 compartment is formed between the first cation exchange membrane and the mono/bivalent high selectivity anion exchange membrane, a desulfurization wastewater 2 compartment is formed between the mono/bivalent high selectivity anion exchange membrane and the second cation exchange membrane, a concentration 3 compartment is formed between the second cation exchange membrane and the anion exchange membrane, and a sodium chloride 4 compartment is formed between the anion exchange membrane and the first cation exchange membrane at the other side; forming a plurality of repeating units of "sodium chloride 1 compartment-desulfurization wastewater 2 compartment-concentration 3 compartment-sodium chloride 4 compartment" between the anode compartment and the cathode compartment;
after passing through a cartridge filter, the desulfurization wastewater filtered by an ultrafiltration membrane system enters a desulfurization wastewater 2 compartment of a mono/divalent anion high-selectivity replacement electrodialysis treatment system, sodium chloride solution is introduced into a sodium chloride 1 compartment and a sodium chloride 4 compartment of replacement electrodialysis, pure water is introduced into a concentration 3 compartment, and replacement electrodialysis treatment is carried out, so that chloride ions and cations in the desulfurization wastewater are enriched in the concentration 3 compartment, and high-concentration chloride salt is obtained;
after the electrodialysis treatment is replaced, the desulfurization wastewater in the desulfurization wastewater 2 compartment is returned to the limestone-gypsum wet desulfurization system for recycling;
after the electrodialysis treatment is replaced, the chloride solution in the concentrated 3 compartments enters the next working procedure for treatment;
step 4, further treatment of the concentrating chamber liquid
The feed liquid in the concentrating 3 compartments is output to an evaporation crystallization system through a pipeline for evaporation to obtain solid salt, and the liquid obtained by evaporation is returned to the concentrating 3 compartments, so that the water circulation in the whole limestone-gypsum wet desulfurization system is realized.
2. The method for treating desulfurization wastewater of a thermal power plant by mono/divalent anion high selectivity displacement electrodialysis according to claim 1, wherein: in the step 1, the medicines for adding the drugs for flocculation sedimentation are PAM and PAC.
3. The method for treating desulfurization wastewater of a thermal power plant by mono/divalent anion high selectivity displacement electrodialysis according to claim 1, wherein: in the step 2, the ultrafiltration membrane in the ultrafiltration membrane system is a hollow fiber ultrafiltration membrane, and a pore-size filtration mode driven by lower transmembrane pressure is adopted.
4. The process for treating desulfurization wastewater of a thermal power plant by mono/divalent anion high-selectivity displacement electrodialysis according to claim 1, wherein the process comprises the following steps: in step 3, the mono/dianion high selectivity displacement electrodialysis system further comprises a feed solution storage tank; the feed liquid storage tank comprises an electrode chamber storage tank, a sodium chloride storage tank, a desulfurization waste water storage tank and a concentrating chamber storage tank; the anode chamber and the cathode chamber are connected in series through a pipeline and are communicated with an electrode chamber storage tank; the inlet and the outlet of the desulfurization waste water 2 compartment are communicated with the desulfurization waste water storage tank through pipelines, the inlet and the outlet of the sodium chloride 1 compartment and the sodium chloride 4 compartment are respectively communicated with the sodium chloride storage tank in parallel through pipelines, and the inlet and the outlet of the concentration 3 compartment are respectively communicated with the concentration chamber storage tank through pipelines.
5. The method for treating desulfurization wastewater of a thermal power plant by mono/divalent anion high selectivity displacement electrodialysis according to claim 1, wherein: the mono/divalent highly selective anion exchange membrane is an anion exchange membrane that is permeable only to monovalent anions and blocks permeation of multivalent anions.
6. The method for treating desulfurization wastewater of a thermal power plant by mono/divalent anion high selectivity displacement electrodialysis according to claim 4, wherein: the mono/divalent anion high-selectivity displacement electrodialysis treatment system is also provided with a circulating pump between each compartment and the corresponding feed liquid storage tank; the flow of the circulating pumps of the sodium chloride 1 compartment, the desulfurization wastewater 2 compartment, the concentration 3 compartment and the sodium chloride 4 compartment are matched with each other to replace the electrodialysis membrane assembly, so that the flow rate of the membrane surface is not lower than 3cm/s.
7. The method for treating desulfurization wastewater of a thermal power plant by mono/divalent anion high selectivity displacement electrodialysis according to claim 1, wherein: in the step 4, the evaporation and crystallization system is a forced circulation evaporation crystallizer, an MVR evaporation crystallizer or a multi-effect evaporation and crystallization device.
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