CN112408558A - Anti-scaling electrodialysis system based on pH control and treatment process - Google Patents
Anti-scaling electrodialysis system based on pH control and treatment process Download PDFInfo
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Abstract
The invention relates to an anti-scaling electrodialysis system based on pH control, which comprises an electrodialysis reactor, a fresh water tank, a concentrated water tank, a pH control system and an acid absorption system; the electrodialysis reactor is formed by assembling an anode plate, a membrane stack and a cathode plate in sequence; the membrane stack is formed by alternately arranging cation selective exchange membranes and anion selective exchange membranes to form alternately arranged fresh water channels and concentrated water channels, and polar water channels are respectively arranged at two sides close to the polar plates; the pH control system mainly comprises an acid storage tank, an acid adding pump, a pipeline mixer and an online pH meter, wherein an electrode water outlet of the electrode water tank is connected to an inlet of the pipeline mixer, and the online pH meter is arranged at an inlet end of the pipeline mixer. The invention has the beneficial effects that: the scaling prevention electrodialysis system based on pH control can avoid the scaling of the polar plate in the operation process of the system, realize the scaling-free operation of the electrodialysis system, optimize the operation working condition and improve the water treatment efficiency.
Description
Technical Field
The invention belongs to the technical field of environment-friendly water treatment, and particularly relates to an electrodialysis system and a treatment process for preventing electrodialysis pole plates from scaling through controlling the pH value of polar water.
Background
The electrodialysis technology, which is a water treatment technology developed in the 50 s of the 20 th century, has the characteristics of low energy consumption, small environmental pollution, strong adaptability, durable equipment, easy mechanization realization, high utilization rate and the like, and is widely applied to the fields of electronics, medicines, foods, chemical industry, environmental protection, industry and the like. The applications of electrodialysis technology for wastewater concentration, pure water preparation, acid and alkali recovery, and resource recycling of useful substances in waste liquid are frequently reported.
In the application process of the electrodialysis technology, a great amount of OH is inevitably generated on the surface of a cathode plate-So that the cathode water pH is always kept at a high level. The liquid to be treated (usually wastewater) often contains high-concentration calcium and magnesium ions, and the calcium and magnesium ions enter into the polar water circulation through the permeation process under the action of an electric field, so that a large amount of calcium and magnesium scale deposits are formed on the surface of the cathode plate. The scale attached to the electrode causes the problems of electrode corrosion, electrode resistance increase, electrode surface structure damage, electrodialysis efficiency reduction, extra energy consumption increase and the like, and becomes a difficult problem to be solved urgently in the application process of the electrodialysis process.
In order to solve the scaling problem, the current mainstream technology adopts a method of pre-treatment hardness removal and periodic acid washing to reduce the harm caused by scaling. The hardness removal technology of the pretreatment has more choices, mainly comprises a membrane separation method, a boiling method, a chemical softening method, an ion exchange method and the like, has the problems of complicated steps, higher cost, secondary pollution and the like, and is particularly not beneficial to the treatment of large-volume wastewater. The periodic acid washing method is to remove the generated calcium and magnesium scales by periodic acid washing (usually hydrochloric acid), a large amount of medicament is required in the acid washing process, the continuous operation of an electrodialysis system is interrupted in the acid washing process, and acid waste water is generated after the acid washing process is finished and is difficult to treat. Furthermore, the periodic pickling cannot fundamentally prevent the continuous generation of calcium and magnesium scales, and can only be used as an emergency means for treating the generated calcium and magnesium scales.
Therefore, there is a need to develop a new electrodialysis system, which can avoid scaling of the electrode plates during the operation of the electrodialysis system without softening the incoming water, so that the system can be continuously operated at an optimal level all the time.
Disclosure of Invention
The invention aims to provide an anti-scaling electrodialysis system and a treatment process based on an electrode water channel pH control technology, aiming at the scaling problem of a cathode plate in the power transmission process in the prior electrodialysis technology.
The anti-scaling electrodialysis system based on pH control comprises an electrodialysis reactor, a fresh water tank, a concentrated water tank, a pH control system and an acid absorption system; the electrodialysis reactor is formed by assembling an anode plate, a membrane stack and a cathode plate in sequence; the membrane stack is formed by alternately arranging cation selective exchange membranes and anion selective exchange membranes to form alternately arranged fresh water channels and concentrated water channels, and polar water channels are respectively arranged at two sides close to the polar plates; the pH control system mainly comprises an acid storage tank, an acid adding pump, a pipeline mixer and an online pH meter, wherein a polar water outlet of the polar water tank is connected to an inlet of the pipeline mixer; the acid absorption system mainly comprises an exhaust valve and an acid absorption box, wherein an exhaust port of the polar water box is connected to an inlet of the exhaust valve, and an outlet of the exhaust valve is connected to the acid absorption box.
Preferably, the method comprises the following steps: the concentrated water tank is connected with the concentrated water channel of the membrane stack to form concentrated water circulation.
Preferably, the method comprises the following steps: the fresh water tank is connected with the fresh water channel of the membrane stack to form fresh water circulation.
Preferably, the method comprises the following steps: the polar water tank is connected with the polar water channel of the membrane stack to form polar water circulation.
Preferably, the method comprises the following steps: the acid adding pump is a variable frequency pump.
Preferably, the method comprises the following steps: the acid absorption box is provided with acid absorption liquid.
Preferably, the method comprises the following steps: the hydrogen discharging fan is connected to an air inlet of the water tank.
Preferably, the method comprises the following steps: and a pH meter is arranged in the acid absorption tank.
The treatment process of the anti-scaling electrodialysis system based on pH control comprises the following steps:
s1, continuously circulating polar water and increasing the pH value in the running process of the electrodialysis system;
s2, setting a trigger value of the pH of the polar water by the pH control system; when the pH value of the inlet water of the cathode electrode water is larger than a trigger value, the system automatically adds concentrated acid through an acid adding pump, reads the value of the on-line pH meter again after a period of time, and monitors whether the pH value of the cathode electrode water is regulated in place or not; if the pH value of the inlet water of the cathode electrode is still larger than the trigger value after the acid is added, repeating the steps of adding the acid and monitoring again until the pH value is smaller than the trigger value; if the pH value does not reach the standard after the acid is added for three times, the system gives an alarm and stops adding the acid, and at the moment, the fault source is judged manually;
s3, when the pH value of the anode water is controlled to be at a lower level, the acid gas in the anode water channel overflows the anode water tank along with hydrogen under the action of the hydrogen exhaust fan, then passes through the exhaust valve and is absorbed by the acid absorption tank, a pH meter is arranged in the acid absorption tank to monitor the pH value of the acid absorption liquid, and when the pH value is lower than a set value, the system gives an alarm to prompt the replacement of the acid absorption liquid.
Preferably, the method comprises the following steps: in step S3, the acid absorbing solution is an alkali solution or water.
The invention has the beneficial effects that:
1. the scaling prevention electrodialysis system based on pH control can avoid the scaling of the polar plate in the operation process of the system, realize the scaling-free operation of the electrodialysis system, optimize the operation working condition and improve the water treatment efficiency.
2. The method eliminates the step of removing hardness in pretreatment, and can directly treat high-hardness wastewater; in addition, the pretreatment medicament cost is saved, the water treatment steps are simplified, and the applicable water quality range of the electrodialysis system is expanded.
3. The invention adds a pH control system and an acid absorption system, greatly reduces the acid washing frequency of the electrodialysis membrane stack, can keep the system to continuously and stably run for a long time, and also reduces the discharge amount of acid washing wastewater.
4. The treatment method is simple, easy to control and suitable for different types of electrodialysis systems; the invention can be used as a new system for complete production, and can also be upgraded and reformed on the basis of an old system.
Drawings
FIG. 1 is a working schematic diagram of an anti-scaling electrodialysis membrane stack;
fig. 2 is a schematic diagram of an anti-scaling electrodialysis system based on pH control.
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.
Example one
The scaling control factors are various and mainly comprise water quality, water temperature, flow rate, heat exchange temperature difference, corrosion and scale inhibitor and the like, wherein the pH value is an important index of the water quality, and the scaling tendency of the calcium-magnesium scale can be greatly reduced by reducing the pH value of the treatment fluid. As shown in figure 1, during the operation of the electrodialysis membrane stack, divalent cations (mainly calcium ions and magnesium ions) in adjacent channels enter into the polar water channels through diffusion and ion exchange, and are continuously generated with OH on the surface of the cathode plate-After combination, calcium and magnesium scale deposition is generated and is attached to the surface of the cathode plate. At the moment, the migration rate of the divalent ions in the cathode water is far higher than that of the divalent ions in the anode water, and the divalent ions are rapidly and massively lost in an abnormal way. The pH value of the circulating polar water can be reduced by adding acid into the polar water channel, and the scaling rate is very slow even if the calcium and magnesium concentration in the circulating polar water is high. The migration rate of divalent ions in the anode water and the migration rate of divalent ions in the cathode water are balanced, and most of calciumMagnesium ions will exit the electrodialysis system through the normal concentration route.
Controlling the pH of the polar water at a lower level, the HClO, HCl and Cl of the anode polar water channel2When a large amount of acid gas is transferred from the liquid phase to the gas phase, the acid gas overflows the polar water tank along with the hydrogen under the action of the hydrogen exhaust fan. These spilled gases, which are highly acidic, irritating, oxidizing and corrosive, will contaminate the surrounding environment upon direct evacuation, and therefore need to be completely absorbed by an alkaline absorbent to achieve green and environmentally friendly operation of the electrodialysis system.
The anti-scaling electrodialysis system is additionally provided with a pH control system and an acid absorption system on the basis of the conventional electrodialysis system. Wherein, the pH control system consists of an acid storage tank, an acid adding pump, a pipeline mixer, an online pH meter and a matched control system. The concentrated acid is stored in an acid storage tank and is uniformly mixed with the polar water through an acid adding pump and a pipeline mixer, and the pH value of the circulating polar water is adjusted. The acid adding pump is a variable frequency pump and is remotely controlled by a control system. The online pH meter is arranged in front of the pipeline mixer, and can feed back the pH value of cathode water inflow in real time. The pH control system can control the acid adding amount according to the feedback value of the on-line pH meter, thereby regulating and controlling the pH value of the circulating polar water. The acid absorption system consists of an exhaust valve and an acid absorption box, and acid absorption liquid is placed in the acid absorption box and is periodically replaced according to the absorption effect. An anti-scaling electrodialysis system based on pH control is shown in fig. 2.
The pH control system is used as a part of the electrodialysis control system and is kept in a normally open state during the operation of the electrodialysis system. The trigger value for the pH of the very water is set (e.g. pH 5.0), i.e. continuous operation is maintained with the very water pH always below the trigger value.
In the operation process of the electrodialysis system, polar water is continuously circulated and the pH value is gradually increased. When the pH value of the inlet water of the cathode electrode water is larger than the trigger value, the system automatically adds concentrated acid with a set volume (for example, 0.1L) through an acid adding pump, reads the value of the pH meter again after a set time (for example, 10 minutes), and monitors whether the pH value of the electrode water is adjusted in place. And if the pH value of the polar water is still larger than the trigger value after the acid is added, repeating the steps of adding the acid and monitoring again until the pH value is smaller than the trigger value. After the acid is added for three times, the pH value does not reach the standard, the system gives an alarm and stops adding the acid, and the fault source needs to be judged manually at the moment. The acid storage tank is provided with a high liquid level alarm and a low liquid level alarm. A pH meter is arranged in the acid absorption tank to monitor the pH value of the acid absorption solution, and when the pH value is lower than a set value (for example, pH 9.0), the system gives an alarm to prompt replacement of the acid absorption solution. The acid absorbing solution may be an alkaline solution (e.g., 30% sodium hydroxide solution) or water. The pH value of the polar water is adjusted by the method, the pH value of the polar water can be kept in a lower range, the cathode plate is kept to run without scaling, and the overall efficiency of an electrodialysis system is ensured.
Example two
The desulfurization wastewater is concentrated and reduced by an electrodialysis system in a certain coal-fired power plant, and is not softened before entering the system, so that the calcium ion concentration and the magnesium ion concentration are higher. The specific water quality conditions are shown in the following table:
the electrodialysis system used a 3% sodium chloride solution as the polar water. Because the hardness of the desulfurization wastewater is high, calcium ions and magnesium ions can penetrate through the polar membrane under the action of an electric field and the permeation action, so that the hardness of the desulfurization wastewater in polar water is rapidly increased. The newly prepared polar water in a certain treatment process has the calcium ion concentration of 9mg/L and the magnesium ion concentration of 3mg/L, and after 5 hours of treatment, the calcium ion concentration is increased to 1377mg/L and the magnesium ion concentration is increased to 259 mg/L. After 7 days of operation, the electrodialysis membrane stack was opened to find that a layer of white scale of about 0.5cm was adhered to the cathode plate, and the scale was analyzed to have a main component of Mg (OH)2And Ca (OH)2. During continuous operation, the electrodialysis current efficiency is continuously reduced from 0.72 initially to 0.45, and the concentration effect of the desulfurization wastewater is continuously deteriorated along with the continuous increase of the temperature rise of the system. In addition, the electrodialysis system of the power plant performs acid cleaning every 7 days, about 30L of concentrated hydrochloric acid is consumed in each acid cleaning, about 1t of acid cleaning wastewater is generated, and a large environment-friendly pressure exists.
And then, the original electrodialysis system is modified, an electrode water pH control system and a terminal acid absorption system are added, and the process route is shown in figure 2. The pH trigger value is set to be 5.0, and 500mL of concentrated hydrochloric acid is automatically added when the pH of cathode inlet water is less than 5.0. Continuously operating for 1 month, always keeping the pH value of the polar water to fluctuate within the range of 2.5-5.0, and monitoring to obtain the electrodialysis current efficiency fluctuating within the range of 0.70-0.75. The difference between the calcium ion concentration and the magnesium ion concentration of the polar water in the operation process and before modification is not large, and no obvious scale is found on the detection polar plate after the operation is finished. 30% sodium hydroxide solution is placed in the acid absorption tank as acid absorption liquid, and the pH value of the acid absorption liquid is reduced from 14.8 to 14.6 in the operation process and does not reach the replacement standard of the acid absorption liquid.
The novel electrodialysis system of the power plant is normally operated for 6 months, the electrode polar plate is not subjected to large-area scaling, the pickling is not carried out, the current efficiency is stably maintained at a high level, and the concentration and decrement effects of the desulfurization wastewater are remarkable. The above results show that the anti-scaling electrodialysis system based on pH control has good applicability.
Claims (10)
1. An anti-scaling electrodialysis system based on pH control is characterized in that: comprises an electrodialysis reactor, a fresh water tank, a concentrated water tank, a pH control system and an acid absorption system; the electrodialysis reactor is formed by assembling an anode plate, a membrane stack and a cathode plate in sequence; the membrane stack is formed by alternately arranging cation selective exchange membranes and anion selective exchange membranes to form alternately arranged fresh water channels and concentrated water channels, and polar water channels are respectively arranged at two sides close to the polar plates; the pH control system mainly comprises an acid storage tank, an acid adding pump, a pipeline mixer and an online pH meter, wherein a polar water outlet of the polar water tank is connected to an inlet of the pipeline mixer; the acid absorption system mainly comprises an exhaust valve and an acid absorption box, wherein an exhaust port of the polar water box is connected to an inlet of the exhaust valve, and an outlet of the exhaust valve is connected to the acid absorption box.
2. The pH control based scaling prevention electrodialysis system according to claim 1, wherein: the concentrated water tank is connected with the concentrated water channel of the membrane stack to form concentrated water circulation.
3. The pH control based scaling prevention electrodialysis system according to claim 1, wherein: the fresh water tank is connected with the fresh water channel of the membrane stack to form fresh water circulation.
4. The pH control based scaling prevention electrodialysis system according to claim 1, wherein: the polar water tank is connected with the polar water channel of the membrane stack to form polar water circulation.
5. The pH control based scaling prevention electrodialysis system according to claim 1, wherein: the acid adding pump is a variable frequency pump.
6. The pH control based scaling prevention electrodialysis system according to claim 1, wherein: the acid absorption box is provided with acid absorption liquid.
7. The pH control based scaling prevention electrodialysis system according to claim 1, wherein: the hydrogen discharging fan is connected to an air inlet of the water tank.
8. The pH control based scaling prevention electrodialysis system according to claim 1, wherein: and a pH meter is arranged in the acid absorption tank.
9. A treatment process for a pH control based scaling prevention electrodialysis system according to claim 1, comprising the steps of:
s1, continuously circulating polar water and increasing the pH value in the running process of the electrodialysis system;
s2, setting a trigger value of the pH of the polar water by the pH control system; when the pH value of the inlet water of the cathode electrode water is larger than a trigger value, the system automatically adds concentrated acid through an acid adding pump, reads the value of the on-line pH meter again after a period of time, and monitors whether the pH value of the cathode electrode water is regulated in place or not; if the pH value of the inlet water of the cathode electrode is still larger than the trigger value after the acid is added, repeating the steps of adding the acid and monitoring again until the pH value is smaller than the trigger value; if the pH value does not reach the standard after the acid is added for three times, the system gives an alarm and stops adding the acid, and at the moment, the fault source is judged manually;
s3, when the pH value of the anode water is controlled to be at a lower level, the acid gas in the anode water channel overflows the anode water tank along with hydrogen under the action of the hydrogen exhaust fan, then passes through the exhaust valve and is absorbed by the acid absorption tank, a pH meter is arranged in the acid absorption tank to monitor the pH value of the acid absorption liquid, and when the pH value is lower than a set value, the system gives an alarm to prompt the replacement of the acid absorption liquid.
10. The pH control based scaling prevention electrodialysis system treatment process according to claim 9, characterized in that: in step S3, the acid absorbing solution is an alkali solution or water.
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| 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 |
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