CN109250846B - Salt-containing wastewater treatment system for inhibiting scaling - Google Patents
Salt-containing wastewater treatment system for inhibiting scaling Download PDFInfo
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- CN109250846B CN109250846B CN201811214419.1A CN201811214419A CN109250846B CN 109250846 B CN109250846 B CN 109250846B CN 201811214419 A CN201811214419 A CN 201811214419A CN 109250846 B CN109250846 B CN 109250846B
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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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
- C02F1/469—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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Abstract
A scale-inhibiting salt-containing wastewater treatment system comprising at least a wastewater reduction unit for obtaining a first concentration concentrated brine and a second concentration concentrated brine having different salt contents from each other, and an electrodialysis unit configured to: the first concentration concentrated brine and the second concentration concentrated brine respectively enter the plurality of concentrated water chambers and the plurality of fresh water chambers in a pressure difference mode, wherein the ion exchange membrane can be shifted by a first distance along a first direction parallel to a connecting line of the cathode and the anode based on the pressure difference to form a first working state, the ion exchange membrane can be shifted by a second distance along a second direction parallel to the connecting line of the cathode and the anode based on the change of the pressure difference to form a second working state, and the first working state and the second working state are switched under the condition that the conductivity of the concentrated water chambers and/or the conductivity of the fresh water chambers are higher than a certain threshold value. The invention can dynamically change the form of the ion exchange membrane and effectively inhibit the generation of scale.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a salt-containing wastewater treatment system for inhibiting scaling.
Background
Liquid desalination techniques have been widely industrialized, including ion exchange techniques, reverse osmosis techniques, and electro-desalination techniques. The electrodialysis technology is a mature electro-desalting technology with early development, and industrialization is firstly realized in foreign countries in the beginning of the twentieth century. On the basis, electrodialysis and ion exchange technology are organically combined, and a novel electric desalting technology is developed.
At present, various electric desalting technologies are widely applied to brackish water desalting, seawater desalting and industrial water treatment to prepare primary pure water, and are also useful for organic material desalting such as: xylitol desalination, whey desalination, biochemical product desalination, dye desalination, and the like.
The electric desalting technology is that under the action of DC electric field, the charged ions in solution permeate through the separating membrane, and the solvent and the non-ionized particles are retained on one side of the membrane to reach the aim of desalting. In the electric desalting technology, the scaling of the device is particularly interesting, particularly on the negative membrane side of a concentration chamber, concentration polarization of scaling-prone ions is easily formed, so that scaling is formed on the surface of the negative membrane, the desalting efficiency is influenced, and the service life of the electric desalting device is shortened.
In the prior art, the conventional operation is reverse polarity, that is, in the operation process of the electric desalting device, the polarity of the electrodes of the device is periodically reversed, the original anode is changed into the cathode, the original cathode is changed into the anode, and the corresponding concentration chamber and the desalting chamber of the original electric desalting device are also reversed, so that the purposes of eliminating membrane surface concentration polarization and inhibiting scaling are achieved. However, the reverse electrode operation is no matter what the brackish desalination is to prepare drinking water or tap water desalination to prepare pure water, only some raw water is lost in the reverse electrode process, but raw material liquid is lost in organic material desalination, which is not allowed, only the non-reverse electrode operation can be adopted, the intermittent operation is adopted, the machine is stopped after one batch of desalination, and the system is subjected to acid cleaning, so that the negative effects of complex operation, unstable desalination performance, short service life of an ion exchange membrane and the like are brought. Another conventional practice is to adjust the ion concentration of the recycled concentrate to a concentration level that reduces the concentration polarization and the potential for fouling.
Patent document CN101543730 discloses a system comprising an electrodialyzer, a stock solution storage tank and a desalting material storage tank, wherein the electrodialyzer comprises anion-cation exchange membranes alternately arranged between positive and negative electrodes, one side of the positive electrode is an anode chamber, one side of the negative electrode is a cathode chamber, desalting chambers and concentrating chambers are alternately formed between the anode chamber and the cathode chamber, the concentrating chambers and the anode chamber of the electrodialyzer are connected with a softened water tank, the other end of the anode chamber is communicated with one end of a softened water inlet of the concentrating chamber, and produced water of the desalting chambers is input into the desalting material storage tank. The cathode chamber, the concentration chamber and the anode chamber are all connected with an external softened water tank, softened water is input into the cathode chamber, the concentration chamber and the anode chamber, part of inlet water of the concentration chamber of the electrodialyzer is circularly supplied by concentrated solution, and the other part of inlet water is supplied by the softened water tank, so that the possibility of scaling is reduced, the structure is simple, and the operation is convenient. The outlet of the anode chamber is connected with a pipeline, the other end of the pipeline is connected with the inlet of the concentration chamber, and the circulating water in the anode chamber is input into the concentration chamber through the pipeline by utilizing the water pressure in the electrodialyzer as a part of the inlet water of the concentration chamber. The possibility of scaling is reduced by removing part of ions in the salt-containing wastewater in a manner of softening the wastewater, the ion exchange membrane does not fundamentally start from the ion exchange membrane, and the ion exchange membrane still has a large scaling risk.
Disclosure of Invention
The word "module" as used herein describes any type of hardware, software, or combination of hardware and software that is capable of performing the functions associated with the "module".
In view of the deficiencies of the prior art, the present invention provides a scale-inhibiting salt-containing wastewater treatment system comprising at least an electrodialysis unit downstream of a wastewater reduction unit. The wastewater reduction unit is configured to: obtaining at least a first concentration concentrated brine and a second concentration concentrated brine having different salt contents from each other based on the first reverse osmosis device, the second reverse osmosis device, and/or a combination of the two, wherein the electrodialysis unit is configured to: the first concentration concentrated brine and the second concentration concentrated brine respectively enter a plurality of concentrated water chambers and fresh water chambers in a pressure difference mode, wherein an ion exchange membrane between the adjacent concentrated water chambers and fresh water chambers can be shifted by a first distance along a first direction parallel to a connecting line of a cathode and an anode based on the pressure difference to form a first working state, the ion exchange membrane can be shifted by a second distance along a second direction parallel to the connecting line of the cathode and the anode based on the change of the pressure difference to form a second working state, and the conductivity of the concentrated water chambers and/or the conductivity of the fresh water chambers is higher than a threshold M1In the case of (2), switching between the first operation mode and the second operation mode is realized.
According to a preferred embodiment, the concentration of the concentrated brine at the first concentration is greater than the concentration of the concentrated brine at the second concentration, and the concentrated brine at the second concentration enters the fresh water chamber. The ion exchange membrane defining the dilute chamber is configured to be deviated in the first and second directions, respectively, when the first concentrated brine enters the concentrated brine chamberMove to form a first maximum distance D between each other1The ion exchange membranes defining the concentrate chambers are moved in an opposing manner in the first and second directions, respectively, to form a first minimum distance D therebetween2Wherein the first maximum distance D1And the first minimum distance D2Defining said first operating configuration.
According to a preferred embodiment, in the case where the concentration of the first concentrated brine is greater than the concentration of the second concentrated brine, and the second concentrated brine enters the dilute chamber and the first concentrated brine enters the concentrate chamber, the ion exchange membranes defining the concentrate chamber are moved in a diverging manner in the first and second directions, respectively, to form a second maximum distance D between each other4The ion exchange membranes defining the dilute chambers are moved in an opposing manner in the first and second directions, respectively, to form a second minimum distance D therebetween3Wherein the second maximum distance D4And said second minimum distance D3Defining said second operating configuration.
According to a preferred embodiment, said first maximum distance D1The first minimum distance D2The second minimum distance D3And said second maximum distance D4Satisfy the relation: d1+D2＝D3+D4。
According to a preferred embodiment, the salt-containing wastewater of the first concentration and the salt-containing wastewater of the second concentration enter the electrodialysis unit at a first flow rate and a second flow rate, respectively, to define the pressure difference between the concentrate chamber and the dilute chamber, wherein the electrodialysis unit operates in the second operating configuration when the water pressure of the concentrate chamber is greater than the water pressure of the dilute chamber, and operates in the first operating configuration when the water pressure of the concentrate chamber is less than the water pressure of the dilute chamber.
According to a preferred embodiment, the salt-containing wastewater treatment system further comprises a wastewater softening unit, a tubular microfiltration unit and a dosing unit, wherein the wastewater softening unit at least comprises a homogenizing water tank, a coagulation tank, a flocculation tank, a sedimentation tank, a first filter and a first intermediate water tank, and the homogenizing water tank, the coagulation tank and the flocculation tank are all communicated with the dosing unit to soften salt-containing wastewater. Salt-containing wastewater passes through the homogenizing water tank, the coagulating basin, the flocculating basin, the sedimentation basin and the first filter in sequence to obtain salt-containing wastewater softening liquid, and the salt-containing wastewater softening liquid is transmitted to the first middle water tank for collection and storage.
According to a preferred embodiment, the wastewater reduction unit comprises at least a first reverse osmosis unit, a second intermediate water tank and a third intermediate water tank, wherein the salt-containing wastewater softener is fed into the first reverse osmosis unit in a first state to obtain the first concentration concentrated brine, and the salt-containing wastewater softener is fed into the second reverse osmosis unit in a second state to obtain the second concentration concentrated brine. And the first concentration concentrated salt solution and the second concentration concentrated salt solution are respectively transmitted to the second middle water tank and the third middle water tank for centralized storage. The first state and the second state both comprise at least a water inlet pressure state when entering the reverse osmosis device corresponding to each state.
According to a preferred embodiment, the electrodialysis cell contains at least one electrodialyser, wherein the electrodialyser comprises a number of membrane stack units comprising n first ion exchange membranes and n +1 second ion exchange membranes, wherein n ≧ 1. The first and second ion exchange membranes are arranged in a spaced-apart manner to define first and second compartments. The first and second ion exchange membranes are defined by the anion exchange membrane and the cation exchange membrane. The first and second compartments are defined by the concentrate and dilute chambers.
According to a preferred embodiment, the concentrated brine of the first concentration and the concentrated brine of the second concentration are fed to the electrodialysis unit separately filtered through the tubular microfiltration unit.
According to a preferred embodiment, said first and second concentrated brines are able to enter said first and second compartments, respectively, in a third and fourth state, respectively, in a switched flow direction, in case of switching the working properties of the first and second compartments based on exchanging the cathodes and anodes of the electrodialyser.
The invention has the beneficial technical effects that:
(1) according to the salt-containing wastewater treatment system, the scales accumulated on the ion exchange membranes can be eliminated in time by dynamically adjusting the forms of the ion exchange membranes, the scales accumulated in the state that the distances between the ion membranes of the concentrated water chamber or the fresh water chamber are small can be eliminated by increasing the distance between the ion membranes of the concentrated water chamber or the fresh water chamber, and the scales of the ion exchange membranes can be effectively inhibited.
(2) The ion exchange membrane is dynamically adjusted, and the cathode and the anode are exchanged to exchange the concentrated water chamber and the fresh water chamber, so that the fresh water chamber and the concentrated water chamber are in an alternate working state, and scaling can be further inhibited or eliminated.
(3) The invention changes the shape of the ion exchange membrane to enable the ion exchange membrane to present an outward convex shape, increases the contact surface of the ion exchange membrane and the strong brine and has higher concentration treatment efficiency.
Drawings
FIG. 1 is a schematic diagram of the modular construction of a preferred saline wastewater treatment system of the present invention;
FIG. 2 is a schematic view of an operating mode of the electrodialyser according to the preferred embodiment of the invention;
FIG. 3 is a schematic view of another operating mode of the electrodialyser according to the preferred embodiment of the invention;
FIG. 4 is a schematic view of the preferred process flow of salt-containing wastewater of the present invention;
FIG. 5 is a first operational configuration of a preferred membrane stack unit of the present invention;
FIG. 6 is a second operational configuration of a preferred membrane stack unit of the present invention; and
fig. 7 is a schematic diagram of the connection relationship of the electronic components of the modules of the present invention.
List of reference numerals
1: wastewater softening unit 2: wastewater reduction unit 3: electrodialysis unit
4: tubular microfiltration unit 5: a dosing unit 6: membrane stack unit
101: the homogenizing water tank 102: a coagulation tank 103: flocculation basin
104: a sedimentation tank 105: the first filter 106: first intermediate pool
201: first reverse osmosis device 202: the second reverse osmosis apparatus 203: second intermediate pool
204: third intermediate pool 301: the electrodialyzer 302: fourth intermediate water pool
303: anion exchange membrane 304: cation exchange membrane 305: cathode electrode
306: anode 307: the concentrated water chamber 308: fresh water chamber
309: the housing 310: water inlet 311: water outlet
601: the first booster pump 602: the second booster pump 603: first direction valve
604: second direction change valve 605: first exchanger tube 606: second exchange tube
607: conductivity sensor 608: the central processing unit 609: third change valve
610: the fourth direction valve 611: first flow rate control valve 612: second flow rate control valve
Detailed Description
The following detailed description is made with reference to the accompanying drawings.
Example 1
Figure 1 shows a schematic of the modular construction of a saline wastewater treatment system of the present invention. As shown in fig. 1, the wastewater treatment system of the present invention includes at least a wastewater softening unit 1, a wastewater reduction unit 2, an electrodialysis unit 3, a tubular microfiltration unit 4, and a dosing unit 5.
The wastewater softening unit 1 comprises at least a homogenizing water tank 101, a coagulation tank 102, a flocculation tank 103, a sedimentation tank 104, a first filter 105 and a first intermediate water tank 106, wherein the transfer flow of wastewater between the homogenizing water tank 101, the coagulation tank 102, the flocculation tank 103 and the sedimentation tank 104 can be provided with a transfer driving force by several lift pumps. The homogenizing tank 101 is used to improve the non-uniformity of the components of the dispersed substances in the wastewater, and can generate relative motion of the wastewater in the homogenizing tank by means of stirring or ultrasonic vibration, for example, to form a mixing and stirring effect. Preferably, the wastewater may be pretreated by adding sodium hydroxide or sodium carbonate, for example, to the homogenizing tank. The coagulation tank 102 is used for coagulation treatment of wastewater, and specifically, a large amount of flocculation may be formed after the coagulant is sufficiently mixed with the wastewater by adding, for example, the coagulant in combination with sufficient stirring. The flocculation tank 103 is used for flocculation treatment of wastewater, and specifically, a large amount of flocculation groups in the wastewater treated by the coagulation tank can be formed into large and compact alum flocs by adding, for example, a flocculating agent. The sedimentation tank 104 is used for standing and settling the wastewater so as to enable large-particle substances in the wastewater to sink to the bottom of the tank, and then sludge is formed after uniform collection and is discharged from the original wastewater so as to achieve the purpose of purifying the water quality. The first filter 105 may be a filter element filter or a high-strength filtering membrane module, and can primarily filter impurities such as suspended matters and colloids in the wastewater based on the first filter to improve the cleanliness of the wastewater, so that the wastewater is not easy to pollute membrane elements in subsequent working sections to cause membrane scaling or blockage. The first intermediate reservoir 106 is used for temporarily storing the wastewater filtered by the first filter. The medicine adding unit 5 is used for providing required medicines for the wastewater softening unit, and the medicine adding unit is respectively communicated with the coagulation tank and the flocculation tank through medicine adding pipelines. A dosing control valve can be arranged in the dosing pipeline to control the addition amount of the required medicament.
Referring again to fig. 1, the wastewater reduction unit 2 includes at least a first reverse osmosis apparatus 201, a second reverse osmosis apparatus 202, a second intermediate water tank 203, and a third intermediate water tank 204. The wastewater treated by the wastewater reduction unit 2 can be output at least at a first concentration and a second concentration. Specifically, the wastewater reduction treatment unit 2 may include only one first reverse osmosis device and one second reverse osmosis device, wherein the first reverse osmosis device may perform a first-stage concentration on the wastewater by configuring a medium-pressure reverse osmosis membrane element so that the wastewater has a first concentration, and the second reverse osmosis device may perform a second-stage concentration on the wastewater by configuring a high-pressure reverse osmosis membrane element so that the wastewater has a second concentration. The upstream of the first reverse osmosis device and the upstream of the second reverse osmosis device are communicated with the first middle water tank so as to receive softened wastewater. The downstream of the first reverse osmosis device and the downstream of the second reverse osmosis device are respectively communicated with the second middle water tank and the third middle water tank so as to temporarily store wastewater with the first concentration and wastewater with the second concentration respectively. Preferably, the first concentration and the second concentration are defined according to the salt content in the wastewater. The salt content of the wastewater concentrate obtained by the first reverse osmosis device is lower than that of the wastewater concentrate obtained by the second reverse osmosis device. Preferably, a plurality of stages of concentration units of the first reverse osmosis device and the second reverse osmosis device are formed in series to obtain more wastewater concentration. For example, a first reverse osmosis device and a second reverse osmosis device are connected in series to form a two-stage concentration unit, wastewater treated by the wastewater softening unit passes through the first reverse osmosis device and the second reverse osmosis device in sequence to be concentrated respectively, and wastewater with different concentrations can be obtained from the permeation side of the second reverse osmosis device by changing the water inlet pressure of the first reverse osmosis device and the water inlet pressure of the second reverse osmosis device. The wastewater reduction unit is used for carrying out primary concentration treatment on the saline wastewater, and the first reverse osmosis device and the second reverse osmosis device are filtering devices based on different membrane modules. For example, the first reverse osmosis unit may employ a medium pressure permeate membrane element and the second reverse osmosis unit may employ a high pressure permeate membrane element.
Referring to fig. 1 again, the tubular microfiltration unit 4 is a filtration assembly formed based on a tubular microfiltration membrane, and the tubular microfiltration unit is communicated with the wastewater reduction unit and the electrodialysis unit, so that the wastewater treated by the wastewater reduction unit is filtered again to remove pollutants in the wastewater, and the wastewater enters the electrodialysis unit, and the protection of a membrane element of the electrodialysis unit can be improved. Specifically, the tubular microfiltration units are respectively communicated with the second middle water tank and the third middle water tank in a one-to-one correspondence mode so as to filter the wastewater in the second middle water tank and the third middle water tank. Preferably, the tubular microfiltration unit may be located upstream of the second intermediate water basin and the third intermediate water basin.
The electrodialysis unit 3 comprises at least an electrodialyser 301 with electrically driven membranes and a fourth intermediate water basin 302, wherein the electrodialyser 301 is in communication upstream with the second intermediate water basin and the third intermediate water basin, respectively, to receive the wastewater of the first concentration and the wastewater of the second concentration conveyed thereby. The downstream of the electrodialyser 301 is connected to a fourth intermediate basin, so that the wastewater further concentrated by the electrodialyser is collected in the fourth intermediate basin.
As shown in fig. 2, the electrodialyzer 301 comprises at least an anion exchange membrane 303, a cation exchange membrane 304, a cathode 305, an anode 306, a concentrate chamber 307, and a dilute chamber 308 built in its casing 309. The anion exchange membranes and the cation exchange membranes are arranged between the cathode and the anode in a staggered mode, and a concentrated water chamber and a dilute water chamber are defined between the cathode and the anode. A water inlet 310 and a water outlet 311 are arranged on the concentrated water chamber and the fresh water chamber. The upstream wastewater enters the electrodialyser through the water inlet 310 and exits the electrodialyser through the water outlet 311.
For ease of understanding, the wastewater treatment process of the saline wastewater treatment module will be discussed in detail.
After the salt-containing wastewater enters the homogenizing water tank 101 through a pipeline and is subjected to homogenization treatment in a stirring manner, a softener of sodium carbonate or sodium hydroxide is applied through a dosing unit to soften the salt-containing wastewater so as to obtain first salt-containing wastewater. The first salt-containing wastewater enters the coagulation tank 102 through a pipeline, and the dosing unit adds a coagulant into the coagulation tank to treat the first salt-containing wastewater to obtain second salt-containing wastewater. And (3) conveying the second salt-containing wastewater into a flocculation tank 103 through a pipeline, and adding a flocculating agent into the flocculation tank by a dosing unit to treat the second salt-containing wastewater to obtain third salt-containing wastewater. The third salt-containing wastewater is conveyed to a sedimentation tank 104 through a pipeline for sedimentation, and the fourth salt-containing wastewater which is relatively clear at the upper part of the sedimentation tank enters a first intermediate water tank 106 for centralized storage after being filtered by a first filter 105. Preferably, the bottom of the coagulation tank, the flocculation tank and the sedimentation tank can be provided with a sludge discharge port, so that settled impurities accumulated at the bottom of the coagulation tank, the flocculation tank and the sedimentation tank can be discharged in time. The sludge can be dewatered by dewatering equipment after being discharged to obtain a sludge cake and separated water, wherein the separated water can be recycled in a mode of mixing the backflow and the salt-containing wastewater and then entering the wastewater softening unit again.
The fourth salt-containing wastewater is respectively conveyed to the first reverse osmosis device 201 and the second reverse osmosis device 202 through pipelines for reduction and concentration treatment, wherein the fourth salt-containing wastewater enters the first reverse osmosis device at a first water inlet pressure and is concentrated under the action of the first water inlet pressure to obtain a first concentration concentrated brine and first produced water. And the fourth salt-containing wastewater enters the second reverse osmosis device at a second water inlet pressure and is subjected to concentration treatment under the action of the second water inlet pressure to obtain a second concentration concentrated brine and second produced water, wherein the first produced water and the second produced water can be directly conveyed to a user end through pipelines to be used and treated as domestic water or irrigation water, for example. The first concentration concentrated salt solution and the second concentration concentrated salt solution are respectively transmitted to a first middle water tank and a second middle water tank 203 through pipelines to be collected and stored.
And under the condition that the concentration of the first-concentration strong brine is higher than that of the second-concentration strong brine, the first-concentration strong brine is conveyed to the fresh water chamber through a pipeline, the second-concentration strong brine is conveyed to the strong water chamber through a pipeline, wherein the first-concentration strong brine is desalted in the fresh water chamber based on ion exchange transfer to obtain third produced water, and the second-concentration strong brine is further concentrated in the strong water chamber based on the ion received from the fresh water chamber to form third-concentration strong brine. The third produced water can be directly delivered to the user end through a pipeline to be used and treated as domestic water or irrigation water. The concentrated brine with the third concentration can be subjected to salt separation treatment by a lower-level device, for example, the concentrated brine with the third concentration can be separated and extracted by an evaporation crystallization device to obtain a fractionated salt.
Preferably, the anion exchange membrane and the cation exchange membrane are selected based on the salt content in the wastewater, for example, when NaCl in the wastewater is to be filtered, the anion exchange membrane is a chloride ion-based exchange membrane, and the cation exchange membrane is a sodium ion-based exchange membrane.
Preferably, switching the operational property of the first or second compartment is to change its treatment of the wastewater. For example, where the first compartment is a concentrate compartment and the second compartment is a dilute compartment, the concentrate compartment operates to increase the salt content of the wastewater flowing therethrough as the wastewater is treated, and the dilute compartment operates to decrease the salt content of the wastewater flowing therethrough as the wastewater is treated. In the case where only the cathode and the anode are exchanged without changing the position of the ion exchange membrane, the concentrate chamber may be switched to the fresh water chamber, and the fresh water chamber may be switched to the concentrate chamber, thereby realizing the exchange between the two.
Example 2
This embodiment is a further improvement of embodiment 1, and repeated contents are not described again.
Fig. 2 and 3 show the operating modes of two different modalities of electrodialysers. As shown in fig. 2 and 3, the electrodialyzer 301 has a cathode 305 and an anode 306 corresponding to each other, wherein the anode is disposed at the left end of a casing 309 and the cathode is disposed at the right end of the casing. Two anion exchange membranes and two cation exchange membranes which are arranged at intervals in a staggered manner are arranged between the cathode and the anode. In the direction extending from the anode to the cathode, there are sequentially a cation exchange membrane, an anion exchange membrane, a cation exchange membrane, and an anion exchange membrane, so that two concentrate chambers 307 are defined by the anion exchange membrane and the cation exchange membrane, which are mirror symmetric with respect to the dilute chamber 308.
Preferably, the distance between the anion-exchange membrane and the cation-exchange membrane adjacent to each other can be adjusted. As shown in fig. 2, 5 and 6, in the first configuration, the anion exchange membrane and the cation exchange membrane defining the fresh water chamber both have a convex configuration, and the anion exchange membrane and the cation exchange membrane defining the concentrated water chamber both have a concave configuration, so that the fresh water chamber has a maximum first width D1The concentrate chamber has a minimum second width D2Wherein the first width D1Is greater than the second width D2. As shown in fig. 3, in the second form, both the anion exchange membrane and the cation exchange membrane defining the dilute chamber are concave, and both the anion exchange membrane and the cation exchange membrane defining the concentrated chamber are convexState such that the fresh water chamber has a minimum third width D3The concentrate chamber has a maximum fourth width D4Wherein the fourth width D4Is greater than the third width D3. Preferably, the first width, the second width, the third width and the fourth width satisfy the relation D1+D2＝D3+D4. Based on the difference of the pressure difference between the water inlet and the water outlet, the anion exchange membrane or the cation exchange membrane is not in an ideal symmetrical parabolic shape after being bent, but is in an asymmetrical bent shape. For the reasons mentioned above, relation D1+D2＝D3+D4There can be some error.
Preferably, the distance between the anion exchange membrane and the cation exchange membrane can be adjusted by controlling the pressure difference applied thereto. For example, in the first configuration, the pressure of the fluid in the dilute chamber is higher than the pressure in the concentrate chamber adjacent to it. The higher pressure in the dilute chamber causes its anion and cation exchange membranes to bulge out into the concentrate chamber to assume a convex configuration. The first mode and the second mode can be switched by providing a positive pressure difference or a negative pressure difference between the concentrate chamber and the dilute chamber adjacent to each other. Preferably, the ion exchange membrane is configured to form a pressure difference by adjusting a difference between liquid levels of the concentrated brine in the fresh water chamber and the concentrated brine in the concentrated brine chamber.
Preferably, the degree of curvature of the anion-exchange membrane or the cation-exchange membrane can be calculated simply by the following formula based on the thin plate mechanical theory.
Wherein D ismaxIndicating the maximum displacement that can be achieved by the anion exchange membrane or the cation exchange membrane. C is a constant that is related to the ratio of the width to the length of either the concentrate or dilute chambers, e.g., C can be directly equal to the width/length of the concentrate chamber. P represents the pressure difference to which the ion exchange membrane is subjected. W represents the width of the concentrate or dilute chambers. H represents the length of the concentrated water chamber or the fresh water chamberAnd (4) degree. E represents the elastic modulus of the corresponding ion-exchange membrane. The width direction of the concentrate chamber or the dilute chamber means a direction parallel to a line connecting the anode and the cathode. The length direction of the concentrate chamber or the dilute chamber refers to the flowing direction of the waste water therein.
Preferably, the pressure difference over the ion exchange membrane can be obtained by controlling the flow rate of the water inlet and/or the water outlet. For example, when it is necessary to make the ion exchange membrane project toward the concentrate chamber, the water inlet rate of the dilute chamber side can be increased while the water outlet rate is kept constant, so that the pressure of the dilute chamber side is higher than that of the concentrate chamber side, and the ion membrane projects toward the concentrate chamber side due to the pressure difference. Similarly, when the ion exchange membrane is required to be in a convex shape towards one side of the concentrated water chamber, the water outlet speed of one side of the fresh water chamber can be reduced, and the water inlet speed of the fresh water chamber can be kept unchanged, so that the pressure of one side of the fresh water chamber is higher than that of one side of the concentrated water chamber. Preferably, the pressure difference of the ion-exchange membrane can be applied by a booster pump before the concentrated brine of different concentration enters the electrodialyser.
Preferably, after the ion exchange membrane morphology is switched, additional fluid may be applied in a spray to the concentrate or dilute chambers for a period of time. For example, gas can enter the concentrated water chamber or the dilute water chamber in the form of bubbles through spraying to flush the ion exchange membrane, and the scaling substances can be better cleaned by matching with the change of the form of the ion exchange membrane.
Preferably, when the form of the ion exchange membrane is changed, the polarities of the cathode and the anode are also switched correspondingly. Simultaneously, the strong brine that gets into dense hydroecium and fresh water room also carries out corresponding switching so that the lower salt solution of concentration keeps getting into fresh water room all the time to the form of fresh water room's ion exchange membrane keeps the indent state all the time, thereby makes the stronger brine of concentration get into and carry out further concentration in the dense hydroecium that has bigger size, can effectively reduce the scale deposit of dense hydroecium. For example, a first pressure is applied to a first concentration of concentrated brine by a first pump and a second pressure is applied to a second concentration of concentrated brine by a second pump, wherein the concentration of the first concentrated brine is higher than the concentration of the second concentrated brine and the first pressure is greater than the second pressure. First strong brine gets into in the strong brine room, and second concentration strong brine gets into the fresh water room, and the first pressure based on strong brine room is greater than the second pressure of fresh water room for the ion exchange membrane of fresh water room presents the indent state, and the ion exchange membrane of strong brine room presents the evagination state. At this time, the left side of the housing corresponds to the anode and the right side corresponds to the cathode. When the form of the ion exchange membrane needs to be changed, the cathode and the anode are exchanged, so that the original fresh water chamber is switched into the concentrated water chamber, and the original concentrated water chamber is switched into the fresh water chamber. At the moment, the first-concentration concentrated brine with the first pressure is switched to the concentrated brine chamber under the current condition through the reversing valve, and the second-concentration concentrated brine with the second pressure is switched to the fresh brine chamber under the current condition. Because the second pressure of the current fresh water chamber is smaller than the first pressure of the current concentrated water chamber, the ion exchange membrane of the current fresh water chamber is in a concave state, and the ion exchange membrane of the current concentrated water chamber is in a convex state. The strong brine with lower concentration is always controlled in the fresh water chamber and is combined with electrode exchange, so that the scale of the ion exchange membrane can be further inhibited or eliminated.
Preferably, the pressure difference applied to the ion exchange membrane can be dynamically adjusted according to at least the type of wastewater to be treated, the elastic modulus of the ion exchange membrane and the structure of the ion exchange membrane, so as to avoid shortening the service life of the ion exchange membrane due to an excessively high pressure difference. Preferably, the pressure difference of the ion exchange membrane may be set in a range of 10Pa to 2500 Pa.
Preferably, the morphological change of the ion-exchange membrane can be based on the time period T1The process is carried out. I.e. every time T1The ion exchange membrane is converted from the outward convex state to the inward concave state, or the ion exchange membrane is converted from the inward concave state to the outward convex state. Each time of the form change of the ionic membrane can be carried out in a mode of applying different pressure differences, so that the convex amount of the convex state of two adjacent times is different. For example, when the ion exchange membrane is first switched from the convex state to the concave state, the applied pressure difference is P1Then, when the ion exchange membrane is switched from the inward concave state to the outward convex state, the applied pressure difference is P2。P1And P2Different from each other, so that the amount of the outward protrusion of the ion exchange membrane is different.
Preferably, the time period T for the morphological change of the ion-exchange membrane1May be based on measuring the resistance of the concentrated brine in the concentrate and/or dilute chambers. For example, the electrical resistance of the concentrated brine in the concentrated brine chamber can be monitored in real time, and when the electrical resistance is smaller than a certain threshold, the control unit adjusts the water inlet pressure, the water outlet pressure, the exchange electrode and/or the exchange water inlet type to realize the conversion of the ion exchange membrane form. The dynamic automatic adjustment of the ion exchange membrane form is realized through monitoring, and the scaling can be effectively inhibited.
Example 3
This embodiment is a further improvement on embodiments 1 and 2, and repeated details are not repeated.
FIG. 4 shows another preferred saline wastewater treatment scheme of the present invention. As shown in fig. 4, for convenience of description, one first ion exchange membrane and two second ion exchange membranes and a dilute water chamber and a concentrated water chamber defined by the two first ion exchange membranes are defined as a membrane stack unit 6. N membrane stack units can be set between the cathode and the anode of the electrodialyzer as required, wherein N is more than or equal to 1.
Preferably, the electrodialysis unit further comprises a first booster pump 601, a second booster pump 602, a first reversing valve 603, a second reversing valve 604, N membrane stack units 6, a first exchanger tube 605 and a second exchanger tube 606. The second intermediate water tank can be respectively communicated with the first exchange tube and the second exchange tube through the first booster pump. Preferably, the second intermediate water tank is communicated with the first exchange pipe through the first booster pump and the first reversing valve in the first state in sequence, and the second intermediate water tank can be communicated with the second exchange pipe through the first booster pump and the first reversing valve in the second state in sequence. The third intermediate water tank can be respectively communicated with the first exchange pipe and the second exchange pipe through the second booster pump. Preferably, the third intermediate water tank is communicated with the first exchange pipe through the second booster pump and the second reversing valve in the third state in sequence, and the third intermediate water tank can be communicated with the second exchange pipe through the second booster pump and the second reversing valve in the fourth state in sequence. The concentrated water chamber and the fresh water chamber of each of the N membrane stack units 6 are respectively connected to the first exchange tube and the second exchange tube through pipelines.
Preferably, the electrodialysis unit further comprises a conductivity sensor 607 for monitoring the electrical resistance of the concentrate and/or fresh water chambers of the N membrane stack units and a central processor 608 for controlling the first booster pump, the second booster pump, the first reversing valve and the second reversing valve, wherein the central processor is based on the conductivity sensor that the conductivity value acquired is larger than a threshold value M1The control signals are generated to control the first booster pump, the second booster pump, the first reversing valve and the second reversing valve to work so as to change the shape of the ion exchange membrane in the membrane stack unit.
Preferably, the threshold value M1Empirical parameters may be selected based on wastewater influent metrics in combination with actual conditions, e.g., the threshold M may be set1The concentration was set to 2500. mu.S/cm. When the actually measured conductivity of the concentrated water chamber is more than 2500 muS/cm, the ion exchange membrane can be judged to have the scaling tendency. Or, when the measured conductivity is larger than the last measured conductivity, the scaling tendency can be preliminarily judged, and the first working state and the second working state are exchanged. Specifically, Ca, for example, is easily formed on the vaginal membrane side of the concentrate chamber2+、Mg2+And the concentration polarization of ions which are easy to scale, so that scale is formed on the surface of the cathode membrane, and the probability of scale generation caused by concentration polarization can be reduced by adjusting the conductivity of the concentrated solution which is recycled in the concentrated water chamber to keep the ion concentration in the concentrated solution at a certain concentration level. For example, in the case where the concentration of the scale-liable ions in the concentrate is more than a certain degree, the scale-liable ions are scaled by forming crystal nuclei on the surface of the ion exchange membrane in a manner similar to the growth of the crystal nuclei and growing around the crystal nuclei. The ion exchange membrane can realize the free switching of the first form and the second form, so that the solution environment of concentrated solution at two sides of the ion exchange membrane can be timely adjusted through the change of the form of the ion exchange membrane to destroy the condition of crystal nucleus formation or growth, and the generation of scale formation is inhibited. For example, the closer to the middle position in the width direction of the concentrate chamber, the faster the water flow speed. Under the condition that the concentrated water chamber is switched from a convex shape to a concave shape, ions are generatedThe exchange membrane is closer to the middle position of the concentrated water chamber, and the ion exchange membrane can be washed by water flow with larger force to destroy the formation of crystal nuclei. For example, when the concentrated water chamber is switched from a concave form to a convex form, the volume of the concentrated water chamber is increased, and the water inflow is increased, so that the concentration of ions which are easy to scale in the concentrated water chamber is reduced, and the scaling of the ion exchange membrane can be effectively inhibited. Preferably, the electrodialysis unit further comprises a third 609 and a fourth 610 reversing valve. And the concentrated water chamber and the fresh water chamber of each of the N membrane stack units are respectively connected to a fourth intermediate water tank and a first intermediate water tank through a first pipeline and a second pipeline, wherein the first pipeline and the second pipeline are respectively provided with a third reversing valve and a fourth reversing valve. The third reversing valve is communicated with the second pipeline through a pipeline, and the fourth reversing valve is communicated with the first pipeline through a pipeline. Preferably, the concentrated water chamber can be communicated with the fourth intermediate water tank through the third reversing valve in the fifth state, and the concentrated water chamber can also be communicated with the first intermediate water tank through the third reversing valve in the sixth state. The fresh water chamber is communicated with the first middle water tank through a fourth reversing valve in a seventh state, and the fresh water chamber can also be communicated with the fourth middle water tank through a fourth reversing valve in an eighth state.
Preferably, the first exchange tube and the second exchange tube are also communicated with the respective concentrate chamber and the fresh water chamber of the N membrane stack units through the first flow rate control valve 611 and the second flow rate control valve 612, respectively, so as to control the pressure difference between the concentrate chamber and the fresh water chamber by changing the flow rate.
For ease of understanding, the treatment of saline wastewater will be discussed in detail.
Referring to fig. 4, after the salt-containing wastewater enters the homogenizing water tank 101 through a pipeline and is homogenized in a stirring manner, a softener of sodium carbonate or sodium hydroxide is applied through a dosing unit to soften the salt-containing wastewater to obtain first salt-containing wastewater. The first salt-containing wastewater enters the coagulation tank 102 through a pipeline, and the dosing unit adds a coagulant into the coagulation tank to treat the first salt-containing wastewater to obtain second salt-containing wastewater. And (3) conveying the second salt-containing wastewater into a flocculation tank 103 through a pipeline, and adding a flocculating agent into the flocculation tank by a dosing unit to treat the second salt-containing wastewater to obtain third salt-containing wastewater. The third salt-containing wastewater is conveyed to a sedimentation tank 104 through a pipeline for sedimentation, and the fourth salt-containing wastewater which is relatively clear at the upper part of the sedimentation tank enters a first intermediate water tank 106 for centralized storage after being filtered by a first filter 105. Preferably, the bottom of the coagulation tank, the flocculation tank and the sedimentation tank can be provided with a sludge discharge port, so that settled impurities accumulated at the bottom of the coagulation tank, the flocculation tank and the sedimentation tank can be discharged in time. The sludge can be dewatered by dewatering equipment after being discharged to obtain a sludge cake and separated water, wherein the separated water can be recycled in a mode of mixing the backflow and the salt-containing wastewater and then entering the wastewater softening unit again.
The fourth salt-containing wastewater is respectively conveyed to the first reverse osmosis device 201 and the second reverse osmosis device 202 through pipelines for reduction and concentration treatment, wherein the fourth salt-containing wastewater enters the first reverse osmosis device at a first water inlet pressure and is concentrated under the action of the first water inlet pressure to obtain a first concentration concentrated brine and first produced water. And the fourth salt-containing wastewater enters the second reverse osmosis device at a second water inlet pressure and is subjected to concentration treatment under the action of the second water inlet pressure to obtain a second concentration concentrated brine and second produced water, wherein the first produced water and the second produced water can be directly conveyed to a user end through pipelines to be used and treated as domestic water or irrigation water, for example. The first concentration concentrated salt solution and the second concentration concentrated salt solution are respectively transmitted to a first middle water tank and a second middle water tank 203 through pipelines to be collected and stored.
First concentration strong brine is transmitted to first switching-over valve with first pressure through first booster pump, and second concentration strong brine is transmitted to second switching-over valve with second pressure through the second booster pump, and wherein, the concentration of first concentration strong brine is greater than the concentration of second concentration strong brine, and first pressure is greater than the second pressure. And the first concentration concentrated brine and the second concentration concentrated brine are respectively transmitted to a concentrated water chamber close to the upper side and a fresh water chamber close to the lower side of the membrane stack unit through a first reversing valve and a second reversing valve. Referring to fig. 5, the ion exchange membrane in the concentrate chamber is made to protrude outward based on the first pressure in the concentrate chamber being greater than the second pressure in the dilute chamber. And the electrodialysis produced water and the electrodialysis concentrated water obtained by the treatment of the membrane stack unit are respectively transmitted to the first intermediate water tank and the fourth intermediate water tank through the third reversing valve and the fourth reversing valve.
And under the condition that the conductivity data acquired based on the conductivity sensor is greater than a set threshold value, the central controller controls the first reversing valve, the second reversing valve, the third reversing valve and the fourth reversing valve to switch the working state so as to change the form of the ion exchange membrane. Specifically, the first concentration concentrated brine is processed by the first booster pump and then is transmitted to the fresh water chamber of the membrane stack unit at the lower side in a first pressure form through the first reversing valve, and the second concentration concentrated brine is processed by the second booster pump and then is transmitted to the concentrated water chamber of the membrane stack unit at the upper side in a second pressure form through the first reversing valve. Referring to fig. 6, the ion exchange membrane of the dilute chamber is caused to exhibit a convex configuration based on the first pressure of the dilute chamber being greater than the second pressure of the concentrate chamber. At this moment, the concentration that is greater than the second concentration strong brine in the strong brine room of first concentration strong brine in the fresh water room, it is not conform to concentrated rule to the concentration of the second concentration strong brine of lower concentration, consequently, need exchange the polarity of current negative pole and positive pole in order to make current strong brine room turn into fresh water room for the electrodialyzer can keep the strong brine that the concentration is lower to get into fresh water room all the time, and the ion exchange membrane of fresh water room presents the indent form all the time. The strong brine with higher concentration is always controlled in the convex strong water chamber with larger channel width, so that the scaling of the strong water chamber can be effectively inhibited. And the electrodialysis produced water and the electrodialysis concentrated water obtained by the treatment of the membrane stack unit are respectively transmitted to the first intermediate water tank and the fourth intermediate water tank through the third reversing valve and the fourth reversing valve.
It should be noted that the above-mentioned embodiments are exemplary, and that those skilled in the art, having benefit of the present disclosure, may devise various arrangements that are within the scope of the present disclosure and that fall within the scope of the invention. It should be understood by those skilled in the art that the present specification and figures are illustrative only and are not limiting upon the claims. The scope of the invention is defined by the claims and their equivalents.
Claims (9)
1. A scale-inhibiting salt-containing wastewater treatment system comprising at least an electrodialysis unit (3) downstream of a wastewater reduction unit (2), characterized in that the wastewater reduction unit (2) is configured to: obtaining at least a first and a second concentrated brine having different salt contents from each other based on the first reverse osmosis unit (201), the second reverse osmosis unit (202) and/or a combination of both, wherein,
the electrodialysis unit (3) is configured to:
the first concentration concentrated salt solution and the second concentration concentrated salt solution enter a plurality of concentrated water chambers (307) and fresh water chambers (308) respectively in a mode of having a pressure difference, wherein an ion exchange membrane between the adjacent concentrated water chambers (307) and fresh water chambers (308) can be shifted by a first distance along a first direction parallel to a connecting line of a cathode (305) and an anode (306) based on the pressure difference to form a first working state, the ion exchange membrane can be shifted by a second distance along a second direction parallel to the connecting line of the cathode and the anode based on the change of the pressure difference to form a second working state, wherein,
the conductivity in the concentrate chamber (307) and/or the conductivity in the fresh water chamber (308) is above a threshold value (M)1) In the case of (2), switching between the first operating mode and the second operating mode is effected,
in the case where the concentration of the first concentration strong brine is greater than the concentration of the second concentration strong brine, and the second concentration strong brine enters the dilute water chamber (308), the first concentration strong brine enters the concentrate water chamber (307),
the ion exchange membranes defining the dilute chambers (308) are moved in a diverging manner in the first and second directions, respectively, to form a first maximum distance D from each other1The ion exchange membranes defining the concentrate chambers are moved in an opposing manner in the first and second directions, respectively, to form a first minimum distance D therebetween2Wherein, in the step (A),
by the first maximum distance D1And the first minimum distance D2Defining said first operating configuration.
2. The saline wastewater treatment system according to claim 1, wherein in the case where said first concentrated brine has a concentration greater than that of said second concentrated brine, and said second concentrated brine enters said fresh water chamber (308), and said first concentrated brine enters said concentrated water chamber (307),
the ion exchange membranes defining the concentrate chambers are moved in a diverging manner in the first and second directions, respectively, to form a second maximum distance D between each other4The ion exchange membranes defining the dilute chambers (308) are moved in an opposing manner along the first and second directions, respectively, to form a second minimum distance D therebetween3Wherein, in the step (A),
by the second maximum distance D4And said second minimum distance D3Defining said second operating configuration.
3. The saline waste treatment system of claim 2, wherein said first maximum distance D1The first minimum distance D2The second minimum distance D3And said second maximum distance D4Satisfy the relation: d1+D2＝D3+D4。
4. Salt-containing wastewater treatment system according to claim 3, characterized in that said first and second concentrations of salt-containing wastewater enter said electrodialysis unit (3) at a first and second flow rate, respectively, to define said pressure difference between a concentrate and a dilute chamber,
the electrodialysis unit (3) operates in the second operating mode when the water pressure of the concentrate chamber is greater than the water pressure of the fresh water chamber, and the electrodialysis unit (3) operates in the first operating mode when the water pressure of the concentrate chamber is less than the water pressure of the fresh water chamber.
5. Salt-containing wastewater treatment system according to one of the preceding claims, characterized in that it further comprises a wastewater softening unit (1), a tubular microfiltration unit (4) and a dosing unit (5), wherein,
the wastewater softening unit (1) at least comprises a homogenizing water tank (101), a coagulation tank (102), a flocculation tank (103), a sedimentation tank (104), a first filter (105) and a first intermediate water tank (106), wherein the homogenizing water tank (101), the coagulation tank (102) and the flocculation tank (103) are all communicated with the dosing unit (5) to soften saline wastewater;
salt-containing wastewater softened liquid obtained by sequentially passing through the homogenizing water tank (101), the coagulation tank (102), the flocculation tank (103), the sedimentation tank (104) and the first filter (105) is transmitted to the first intermediate water tank (106) for collection and storage.
6. Saline wastewater treatment system according to claim 5, characterized in that said wastewater reduction unit (2) comprises at least a first reverse osmosis device (201), a second reverse osmosis device (202), a second intermediate water basin (203) and a third intermediate water basin (204), wherein,
the salt-containing wastewater softener in a first state is fed into the first reverse osmosis unit (201) to obtain the first concentration concentrated salt liquor, and the salt-containing wastewater softener in a second state is fed into the second reverse osmosis unit (202) to obtain the second concentration concentrated salt liquor;
the first concentration strong brine and the second concentration strong brine are respectively transmitted to the second intermediate water tank (203) and the third intermediate water tank (204) for collection and storage;
the first state and the second state both comprise at least a water inlet pressure state when entering the reverse osmosis device corresponding to each state.
7. System for treating saline waste water according to claim 5, wherein said electrodialysis cell (3) comprises at least one electrodialyser (301), wherein said electrodialyser (301) comprises a plurality of membrane stack units (6),
the membrane stack unit (6) comprises n first ion exchange membranes and n +1 second ion exchange membranes, wherein the first ion exchange membranes and the second ion exchange membranes are arranged in a spaced mode to define a first compartment and a second compartment, and n is larger than or equal to 1;
the first and second ion exchange membranes are defined by an anion exchange membrane (303) and a cation exchange membrane (304), and the first and second compartments are defined by the concentrate (307) and the dilute (308) chambers.
8. Salt-containing wastewater treatment system according to claim 5, characterized in that said first and second concentrated brine enter said electrodialysis unit (3) in such a way that they are filtered again by said tubular microfiltration unit (4) respectively.
9. The brine wastewater treatment system according to claim 7, wherein said first and second concentrated brines are capable of entering said first and second compartments in a third and fourth state, respectively,
in the case of switching the operating properties of a first and a second compartment based on the exchange electrodialyser cathode and anode, the first and second concentrated brines enter the second and first compartment, respectively, in a flow direction switching manner.
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| PCT/CN2019/073405 WO2020077918A1 (en) | 2018-10-17 | 2019-01-28 | A bipolar-membrane-based brine recycling system |
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| US11855324B1 (en) | 2022-11-15 | 2023-12-26 | Rahul S. Nana | Reverse electrodialysis or pressure-retarded osmosis cell with heat pump |
| US12040517B2 (en) | 2022-11-15 | 2024-07-16 | Rahul S. Nana | Reverse electrodialysis or pressure-retarded osmosis cell and methods of use thereof |
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| CN111954568B (en) * | 2018-10-17 | 2022-04-15 | 倍杰特集团股份有限公司 | Saline water recovery system based on bipolar membrane |
| CN112897652A (en) * | 2021-01-28 | 2021-06-04 | 烟台大学 | Electrodialysis desalination device |
| US11502323B1 (en) | 2022-05-09 | 2022-11-15 | Rahul S Nana | Reverse electrodialysis cell and methods of use thereof |
| US11502322B1 (en) | 2022-05-09 | 2022-11-15 | Rahul S Nana | Reverse electrodialysis cell with heat pump |
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