CN111960513A - Electrodialysis reactor for preventing cathode plate from scaling and wastewater treatment method - Google Patents
Electrodialysis reactor for preventing cathode plate from scaling and wastewater treatment method Download PDFInfo
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- CN111960513A CN111960513A CN202010884278.5A CN202010884278A CN111960513A CN 111960513 A CN111960513 A CN 111960513A CN 202010884278 A CN202010884278 A CN 202010884278A CN 111960513 A CN111960513 A CN 111960513A
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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
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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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
- C02F1/4602—Treatment of water, waste water, or sewage by electrochemical methods for prevention or elimination of deposits
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
Abstract
The invention relates to an electrodialysis reactor for preventing cathode plates from scaling, which comprises an electrodialysis reactor, a fresh water tank, a concentrated water tank and an electrode water tank; the electrodialysis reactor is formed by assembling an anode plate, a membrane stack and a cathode plate in sequence; the arrangement mode of the membrane stack is A2- (C-A)n-C-a2, the fresh water channel and the concentrated water channel being arranged at intervals; wherein: a2 refers to a monovalent selective anion exchange membrane, C refers to a selective cation exchange membrane, a refers to a selective anion exchange membrane; the concentrated water tank, the concentrated water pump, the concentrated water filter and the membrane pile concentrated water channel are sequentially connected to form a concentrated water circulation passage; the fresh water tank, the fresh water pump, the fresh water filter and the membrane stack fresh water channel are sequentially connected to form a fresh water circulation passage. The invention has the beneficial effects that: the electrodialysis reactor for preventing the cathode plate from scaling is utilized to treat the salt-containing wastewater, so that the salt content can be greatly reducedThe concentration of divalent cations (primarily calcium and magnesium) and divalent anions (primarily sulfate) in the low polar water reduces the tendency for cathode plate fouling.
Description
Technical Field
The invention belongs to the technical field of environment-friendly water treatment, and particularly relates to an electrodialysis reactor capable of preventing cathode plates from scaling and a wastewater treatment method.
Background
With the rapid development of modern socioeconomic, the industrial production level is rapidly improved, and the problem of water pollution is increasingly serious. In recent years, with the successive promulgation and implementation of regulations such as "energy saving law" and "environmental protection law", the national requirements for water consumption, water discharge and water quality of discharged water of enterprises are becoming more and more strict, so that the reduction of wastewater discharge and the realization of wastewater resource utilization become important subjects in the field of water treatment.
Electrodialysis is a method of separating particles of different solutes by the permselectivity of an ion exchange membrane under the action of an electric field. And cations and anions in the fresh water chamber pass through the selective membrane and then are enriched in the concentrated water chamber, so that recyclable fresh water with low ion concentration and concentrated water with high ion concentration are obtained, and the concentration and decrement of the wastewater are realized. The electrodialysis technology has the advantages of high efficiency, cleanness, energy conservation, low cost and the like, and is widely applied to industries such as chemical metallurgy, light industry, papermaking, pharmaceutical industry and the like.
When electrodialysis is used in the wastewater concentration process, a large amount of OH inevitably generated at the cathode of the electrodialysis device-If the polar water channel contains calcium ions and magnesium ions, CaCO is easily formed3、Mg(OH)2、Ca(OH)2And precipitating. In addition, if the concentration of sulfate ions in the polar water is high, intractable CaSO may also be formed4And (4) precipitating. The precipitates generated in the polar water channels can be attached to the cathode plate to form cathode plate scaling, which causes electrode corrosion, electrode resistance increase and electrode surface structure damage, thereby reducing the desalination of the systemEfficiency and increase overall energy consumption. Therefore, there is a need to develop a novel electrodialysis reactor, which can avoid the massive enrichment of calcium ions, magnesium ions and sulfate ions in the polar water channel, thereby reducing the scaling tendency of divalent ions on the surface of the cathode plate and ensuring the long-term reliable operation of the electrodialysis system in the wastewater concentration process.
Disclosure of Invention
The invention aims to provide an electrodialysis reactor for preventing cathode scaling and a wastewater treatment method, aiming at solving the problem that a cathode plate is easy to scale in the power transmission process in the prior electrodialysis technology.
The electrodialysis reactor for preventing the cathode plate from scaling comprises an electrodialysis reactor, a fresh water tank, a concentrated water tank and an electrode water tank; the electrodialysis reactor is formed by assembling an anode plate, a membrane stack and a cathode plate in sequence; the arrangement mode of the membrane stack is A2- (C-A)n-C-a2, wherein: n is a natural number of 1-2000, and n +1 fresh water channels, n +1 concentrated water channels and 2 polar water channels are formed and are arranged at intervals; wherein: a2 refers to a monovalent selective anion exchange membrane, C refers to a selective cation exchange membrane, a refers to a selective anion exchange membrane; the concentrated water tank, the concentrated water pump, the concentrated water filter and the membrane pile concentrated water channel are sequentially connected to form a concentrated water circulation passage; the fresh water tank, the fresh water pump, the fresh water filter and the membrane stack fresh water channel are sequentially connected to form a fresh water circulation passage; the polar water tank, the polar water pump, the polar water filter and the membrane stack polar water channel are sequentially connected to form a polar water circulation passage.
Preferably, the method comprises the following steps: the selective cation exchange membrane designated by C is one of common selective cation exchange membranes, monovalent selective cation exchange membranes or other types of cation exchange membranes.
Preferably, the method comprises the following steps: the selective anion exchange membrane designated by A is one of common selective anion exchange membranes, monovalent selective anion exchange membranes or other types of anion exchange membranes.
Preferably, the method comprises the following steps: the two sides of each membrane are respectively provided with a supporting clapboard, and the upper end and the lower end of the clapboard are respectively provided with a water flow hole and a communicating hole.
The method for treating the wastewater of the electrodialysis reactor for preventing the cathode plate from scaling comprises the following steps:
s1, respectively placing the salt-containing wastewater in a concentrated water tank and a fresh water tank, and preparing a sodium chloride solution with the mass fraction of 2.0% -2.5% as polar water;
s2, simultaneously starting a concentrated water pump, a fresh water pump and an electrode water pump, and starting concentrated water circulation, fresh water circulation and electrode water circulation;
s3, after the system runs stably, supplying power to the electrodes of the electrodialysis reactor, adjusting the voltage and the current to proper values, and concentrating the wastewater by an electrodialysis method; under the electric driving action of an electric field and the selective separation action of an ion exchange membrane, ions in the fresh water channel migrate to the concentrated water channel, fresh water with low ion concentration is formed in the fresh water channel, and concentrated water with high ion concentration is formed in the concentrated water channel;
and S4, after a period of time, the ion concentration of the fresh water side is reduced, the ion concentration of the concentrated water side is increased, the treated fresh water is recycled, and the treated concentrated water is subjected to subsequent advanced treatment.
Preferably, the method comprises the following steps: in step S3, the cathode water and the anode water flow out from the electrode water outlet of the electrodialysis reactor, are mixed, and then are circulated and refluxed to the electrode water inlet of the electrodialysis reactor.
The invention has the beneficial effects that:
1. the electrodialysis reactor for preventing the cathode plate from scaling is used for treating the salt-containing wastewater, so that the concentrations of divalent cations (mainly calcium ions and magnesium ions) and divalent anions (mainly sulfate ions) in polar water can be greatly reduced, the scaling tendency of the cathode plate is reduced, the scaling rate of calcium and magnesium scales in the cathode plate is slowed down, and the acid washing frequency is reduced.
2. The method reduces scaling of the cathode plate in the operation process of the system, can reduce electrode resistance, reduce thermal conversion of electric energy, improve electrodialysis ion migration efficiency (namely current efficiency), and improve the ion separation effect of the salt-containing wastewater.
3. The system has the advantages of low cost, reasonable arrangement, simple method, almost no adverse effect and strong applicability, and can be used for treating industrial wastewater which is not softened and complex salt-containing wastewater with different water qualities in various industries.
Drawings
FIG. 1 is a schematic view showing the structure and principle of an electrodialysis reactor (ACA type) for preventing the fouling of cathode plates;
FIG. 2 is a process flow diagram of an anti-scaling electrodialysis wastewater treatment system;
FIG. 3 is a schematic diagram showing the structure and schematic diagram of a conventional electrodialysis reactor (CAC type);
FIG. 4 is a schematic diagram of the anti-scaling electrodialysis reactor for concentrating desulfurization wastewater in the embodiment.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are set forth merely to aid in the understanding of the invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The electrodialysis reactor for preventing the cathode plate from scaling comprises an electrodialysis reactor, a fresh water tank, a concentrated water tank and an electrode water tank. The electrodialysis reactor is assembled by an anode plate, a membrane stack and a cathode plate in sequence, wherein the arrangement mode of the membrane stack is A2- (C-A)nAnd the-C-A2, n is a natural number of 1-2000, and n +1 fresh water channels, n +1 concentrated water channels and 2 polar water channels are formed and are arranged at intervals. Wherein: a2 refers to a monovalent selective anion exchange membrane that allows only monovalent anions to pass through; c broadly refers to a selective cation exchange membrane, which may be a common selective cation exchange membrane, a monovalent selective cation exchange membrane, or other type of cation exchange membrane; a broadly refers to a selective anion exchange membrane, which may be a common selective anion exchange membrane, a monovalent selective anion exchange membrane, or other type of anion exchange membrane. Fig. 1 shows the structure of the electrodialysis reactor and the ion separation effect when n ═ 2, a is a general selective anion-exchange membrane, and C is a general selective cation-exchange membrane.
And supporting partition plates are arranged on two sides of each membrane, so that the effects of supporting protection and shunting are mainly achieved. The upper end and the lower end of the clapboard are respectively provided with a water flow hole and a communication hole which can fix the water flow direction, so that all the fresh water channels and the external fresh water tank form circulation, all the concentrated water channels and the external concentrated water tank form circulation, and two polar water channels and the external polar water tank form circulation.
When the electrodialysis reactor is used for treating salt-containing wastewater, the polar water in the polar water channel is a sodium chloride solution with the mass fraction of 2% -2.5%, wherein the sodium chloride used for preparing the polar water is an analytical pure medicament, and the hardness of the prepared polar water is not more than 30 mg/L. The salt-containing wastewater simultaneously enters the concentrated water channel and the fresh water channel, then the electrodes are operated, the voltage and the current are adjusted to proper values, under the electric driving action of the electric field and the selective separation action of the ion exchange membrane, ions in the fresh water channel migrate towards the concentrated water channel, the fresh water with low ion concentration is formed in the fresh water channel, the concentrated water with high ion concentration is formed in the concentrated water channel, and the ion separation effect of the electrodialysis reactor on the salt-containing wastewater is realized.
In particular, due to the presence of the polar water channel monovalent selective anion exchange membrane: divalent cations (mainly calcium ions and magnesium ions) of the cathode adjacent to the concentrated water channel cannot migrate to the cathode water channel in a large amount, and the rejection rate of the divalent cations exceeds 99%; divalent anions (mainly sulfate ions) of the anode adjacent to the fresh water channel can not be greatly transferred to the anode water channel, and the retention rate of the divalent anions exceeds 98 percent. And the cathode electrode water and the anode electrode water flow out from the electrode water outlet of the electrodialysis reactor, are mixed and then flow back to the electrode water inlet of the electrodialysis reactor in a circulating mode. OH in cathode water-And H in anode water+After the polar water is mixed, a neutralization reaction occurs, so that the pH value of the polar water is basically kept stable. Monovalent anions (mainly Cl) in cathode water-) Will enter into the adjacent concentrated water channel through the ion exchange membrane, and the anode is adjacent to part of monovalent anions (mainly Cl) in the fresh water channel-) Will enter the anode water. After anode electrode water and cathode electrode water are mixed, the ion type and concentration in the anode electrode water are basically kept unchanged, and the concentrations of divalent anions and divalent cations are kept at an extremely low level.
Utilize this electrodialysis reactor that prevents negative plate scale deposit, form novel electrodialysis effluent disposal system in a supporting way, can be used for the concentrated processing who contains salt waste water. As shown in fig. 2, the system consists of an electrodialysis reactor, a concentrated water tank, a fresh water tank, an electrode water tank, a circulating pump, a filter, a heat exchanger and a matched pipeline valve meter. The concentrated water tank, the concentrated water pump, the concentrated water filter and the membrane pile concentrated water channel jointly form concentrated water circulation. The fresh water tank, the fresh water pump, the fresh water filter and the membrane stack fresh water channel jointly form fresh water circulation. The polar water tank, the polar water pump, the polar water filter and the membrane stack polar water channel jointly form polar water circulation.
The salt-containing wastewater treatment method by using the anti-scaling electrodialysis wastewater treatment system comprises the following steps: respectively placing the salt-containing wastewater in a concentrated water tank and a fresh water tank, and preparing a sodium chloride solution with the mass fraction of 2.0-2.5% as polar water. And simultaneously, starting a concentrated water pump, a fresh water pump and an electrode water pump to start concentrated water circulation, fresh water circulation and electrode water circulation. And after the system runs stably, supplying power to the electrodes of the electrodialysis reactor, adjusting the voltage and the current to proper values, and concentrating the wastewater by an electrodialysis method. After a period of time, the ion concentration on the fresh water side is greatly reduced, the ion concentration on the concentrated water side is greatly increased, the treated fresh water can be recycled, and the treated concentrated water can be subjected to subsequent advanced treatment.
For a common electrodialysis system (CAC type, as shown in figure 3), cation exchange occurs between polar water and wastewater in the electrodialysis treatment process, divalent cations in the wastewater migrate into the polar water, and scaling occurs on a cathode plate after the operation for a period of time, so that the current efficiency is reduced, and the wastewater concentration effect is influenced. Common anti-plate fouling strategies include: acid washing, periodic polar water discharge, acid addition for increasing the pH value of the polar water and the like. With the electrodialysis system (ACA type, as shown in FIG. 1) for preventing cathode scaling, only monovalent anion exchange (mainly Cl) occurs between polar water and wastewater during electrodialysis treatment-) After the system runs under the same working condition, the scaling amount of the cathode plate is reduced to 10-15% of the original scaling amount, and the reduction degree of the current efficiency is light when the system runs for a long time.
Example (b):
certain coal fired power plant handles desulfurization waste water with the electrodialysis reactor of this patent that prevents the scale deposit of negative plate, and this desulfurization waste water has got rid of most heavy metal ion through the pretreatment of triplex box system, but calcium ion, magnesium ion, sulfate ion, chloride ion concentration are higher. The specific water quality conditions are shown in the following table.
TABLE 1 desulfurization waste water quality condition table
The rated treatment flow of the configured system is 10 tons/hour, and the system consists of an electrodialysis reactor, a concentrated water tank, a fresh water tank, an electrode water tank, a circulating pump, a filter, a cooling system, corresponding pipelines and valves. The concentrated water, the fresh water and the polar water form three internal circulations through different channels of the membrane stack respectively. The outlet of the system concentrated water pump is connected with a bypass flue gas drying tower, and the concentrated and reduced desulfurization wastewater concentrated water is subjected to evaporation treatment by the original bypass flue gas evaporation system. An outlet of the fresh water pump is connected with a slurry pond in the desulfurization absorption tower area, and fresh water with high sulfate radical concentration and low chloride ion concentration is discharged and returned to the desulfurization system for resource utilization.
The electrodialysis reactor consists of an anode plate, a membrane stack and a cathode plate. The membrane stack is arranged in a monovalent selective anion exchange membrane- (common selective cation exchange membrane-monovalent selective anion exchange membrane)nNamely A2- (C-A2)nAnd n is 80, 80 fresh water channels, 80 concentrated water channels and 2 polar water channels positioned at the outermost side are formed, and the fresh water channels and the concentrated water channels are arranged at intervals. Supporting clapboards are arranged between the ion exchange membranes to ensure the independent and smooth work of the passages of the concentrated water, the fresh water and the polar water. The electrodialysis reactor structure and principle in this example is shown in figure 4.
And desulfurization wastewater in a clarification tank at the outlet of the triple box system of the power plant enters a concentrated water tank and a fresh water tank respectively to serve as initial concentrated water and initial fresh water. A 2.0% mass fraction sodium chloride solution was prepared using 99.5% analytically pure sodium chloride as the initial polar water. Setting the voltage of the electrodialysis reactor as the maximum rated voltage, and continuously operating the system for 168 hours to obtain fresh water with the chloride ion concentration of 3089mg/L and the sulfate ion concentration of 1456mg/L, and concentrated water with the chloride ion concentration of 55267mg/L and the sulfate ion concentration of 784 mg/L. The quality of both the concentrated water and the fresh water accords with the design value of the system, and the aim of concentrating and reducing the desulfurization wastewater is fulfilled. In which the system chloride ion discharge rate reaches 77%, which is a number of improvements compared to 72% of the previous conventional electrodialysis (CAC type) system. Prove that the novel anti-scaling electrodialysis reactor can normally and efficiently carry out desulfurization wastewater treatment and can improve the current efficiency to a certain extent.
It is worth noting that after 168 hours of continuous operation, the calcium ion concentration of the polar water in the polar water tank of the novel electrodialysis system adopted by the utility model is 83mg/L, the magnesium ion concentration is 62mg/L, the sulfate ion concentration is 104mg/L, the surface of the cathode plate is flat, no obvious scale is formed, and acid washing is not needed. In contrast, after a conventional electrodialysis system (CAC type electrodialysis reactor) used in the past was continuously operated for 168 hours, the calcium ion concentration of the polar water in the polar water tank was 2069mg/L, the magnesium ion concentration was 899mg/L, the sulfate ion concentration was 58mg/L, the surface of the cathode plate was covered with a layer of white scale of about 0.5cm, and the analyzed scale sample was Mg (OH)2And CaCO3The electrode pickling needs to be performed immediately. Experiments prove that the novel anti-scaling electrodialysis reactor can effectively prevent scaling of the cathode plate and reduce the pickling frequency.
The anti-scaling electrodialysis system is normally operated for 3 months, 200 tons of desulfurization wastewater are treated every day averagely, and the concentration and decrement effects of the desulfurization wastewater are obvious. The water quality of the polar water is qualified during the operation, and the scaling phenomenon is not found on the polar plate. The above results indicate that the electrodialysis reactor for preventing fouling of the cathode plate has good applicability.
Claims (6)
1. An electrodialysis reactor for preventing cathode plate scaling, which is characterized in that: comprises an electrodialysis reactor, a fresh water tank, a concentrated water tank and a polar water tank; the electrodialysis reactor is formed by assembling an anode plate, a membrane stack and a cathode plate in sequence; the arrangement mode of the membrane stack is A2- (C-A)n-C-a2, wherein: n is a natural number of 1-2000, and n +1 fresh water channels and n +1 concentrated water channels are formedThe device comprises channels and 2 polar water channels, wherein the fresh water channels and the concentrated water channels are arranged at intervals; wherein: a2 refers to a monovalent selective anion exchange membrane, C refers to a selective cation exchange membrane, a refers to a selective anion exchange membrane; the concentrated water tank, the concentrated water pump, the concentrated water filter and the membrane pile concentrated water channel are sequentially connected to form a concentrated water circulation passage; the fresh water tank, the fresh water pump, the fresh water filter and the membrane stack fresh water channel are sequentially connected to form a fresh water circulation passage; the polar water tank, the polar water pump, the polar water filter and the membrane stack polar water channel are sequentially connected to form a polar water circulation passage.
2. Electrodialysis reactor for preventing fouling of cathode plates according to claim 1, characterized in that: the selective cation exchange membrane designated by C is one of common selective cation exchange membranes, monovalent selective cation exchange membranes or other types of cation exchange membranes.
3. Electrodialysis reactor for preventing fouling of cathode plates according to claim 1, characterized in that: the selective anion exchange membrane designated by A is one of common selective anion exchange membranes, monovalent selective anion exchange membranes or other types of anion exchange membranes.
4. Electrodialysis reactor for preventing fouling of cathode plates according to claim 1, characterized in that: the two sides of each membrane are respectively provided with a supporting clapboard, and the upper end and the lower end of the clapboard are respectively provided with a water flow hole and a communicating hole.
5. A method for treating wastewater of an electrodialysis reactor for preventing fouling of cathode plates according to claim 1, wherein: the method comprises the following steps:
s1, respectively placing the salt-containing wastewater in a concentrated water tank and a fresh water tank, and preparing a sodium chloride solution with the mass fraction of 2.0% -2.5% as polar water;
s2, simultaneously starting a concentrated water pump, a fresh water pump and an electrode water pump, and starting concentrated water circulation, fresh water circulation and electrode water circulation;
s3, after the system runs stably, supplying power to the electrodes of the electrodialysis reactor, adjusting the voltage and the current to proper values, and concentrating the wastewater by an electrodialysis method; under the electric driving action of an electric field and the selective separation action of an ion exchange membrane, ions in the fresh water channel migrate to the concentrated water channel, fresh water with low ion concentration is formed in the fresh water channel, and concentrated water with high ion concentration is formed in the concentrated water channel;
and S4, after a period of time, the ion concentration of the fresh water side is reduced, the ion concentration of the concentrated water side is increased, the treated fresh water is recycled, and the treated concentrated water is subjected to subsequent advanced treatment.
6. A method for treating wastewater of an electrodialysis reactor for preventing fouling of cathode plates according to claim 5, wherein: in step S3, the cathode water and the anode water flow out from the electrode water outlet of the electrodialysis reactor, are mixed, and then are circulated and refluxed to the electrode water inlet of the electrodialysis reactor.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113354040A (en) * | 2021-06-04 | 2021-09-07 | 杭州贝思特节能环保科技有限公司 | Salting electrodialysis device and using method thereof |
| CN113651400A (en) * | 2021-09-15 | 2021-11-16 | 西安西热水务环保有限公司 | Electrodialysis device for softening-free pretreatment of desulfurization wastewater |
| JP7001882B1 (en) * | 2021-07-22 | 2022-01-20 | 生態環境部華南環境科学研究所 | Copper pyrophosphate plating Electrodialysis device for highly efficient desalination of wastewater |
| CN114149058A (en) * | 2020-12-10 | 2022-03-08 | 佛山市美的清湖净水设备有限公司 | Membrane stack for water purification unit and water purification unit |
| CN117023733A (en) * | 2023-10-10 | 2023-11-10 | 华南理工大学 | Ion separation device for sea water desalination |
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