CN111675394A - High-salt industrial wastewater resource recovery treatment system and method - Google Patents

High-salt industrial wastewater resource recovery treatment system and method Download PDF

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Publication number
CN111675394A
CN111675394A CN202010603205.4A CN202010603205A CN111675394A CN 111675394 A CN111675394 A CN 111675394A CN 202010603205 A CN202010603205 A CN 202010603205A CN 111675394 A CN111675394 A CN 111675394A
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water
bipolar membrane
membrane electrodialysis
reverse osmosis
induced crystallization
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陆梦楠
赵焰
徐志清
郭旭涛
陈雪
苏双青
杨燕
孙斌
范鑫帝
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Beijing Lucency Enviro Tech Co Ltd
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Beijing Lucency Enviro Tech Co Ltd
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/44—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
    • 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
    • C02F1/4695—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis electrodeionisation
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/427—Treatment of water, waste water, or sewage by ion-exchange using mixed beds
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F2001/5218—Crystallization
    • 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
    • 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
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/02—Softening water by precipitation of the hardness

Abstract

The invention provides a high-salt industrial wastewater resource recovery treatment system and a method, comprising a reverse osmosis device and a bipolar membrane electrodialysis device, wherein an induced crystallization device is arranged between the reverse osmosis device and the bipolar membrane electrodialysis device; the reverse osmosis device is used for concentrating the incoming water, the bipolar membrane electrodialysis device is used for hydrolyzing and ionizing water molecules to form recoverable acid and alkali, and the induced crystallization device is used for removing heavy metal ions and/or Ca of the concentrated incoming water2+So as to meet the liquid inlet requirement of the bipolar membrane electrodialysis device. The invention aims to solve the problem of discharge of industrial wastewater containing high-concentration salt and heavy metal, and combines a reverse osmosis device and a bipolar membrane electrodialysis device, and an induced crystallization is arranged between the reverse osmosis device and the bipolar membrane electrodialysis deviceThe device can obtain high water yield, save water resources, remove hard ions and heavy metal ions in wastewater, reduce the risk of membrane blockage, generate acid and alkali byproducts with high value, and solve the problems of low value of byproduct crystalline salt and limited market demand.

Description

High-salt industrial wastewater resource recovery treatment system and method
Technical Field
The invention relates to the technical field of water treatment, in particular to a high-salt industrial wastewater resource recovery treatment system and method.
Background
Industrial wastewater from metal metallurgy washing wastewater, coal-fired power plant desulfurization wastewater, coal chemical industry end wastewater, highly mineralized mine water and the like often contains high-concentration salt and heavy metal to become a main environmental problem, the high-salt wastewater is a very headache problem in industrial sewage treatment engineering, the treatment effect of the sewage is greatly influenced by the salt due to the traditional biological treatment method, and high-concentration inorganic salt can destroy cell membranes and enzymes in bacteria of microorganisms by increasing the environmental osmotic pressure, so that the physiological activity of the microorganisms is destroyed, the biological treatment of the wastewater generates toxic action, and the treatment effect of a sewage treatment station on the high-salt sewage is greatly reduced and can not reach the national discharge standard. Such wastewater may be treated using physicochemical methods to meet standard requirements prior to discharge to an aqueous environment. However, a large amount of heavy metal water-containing sludge and miscellaneous salt solid waste are generated, the extraction cost of industrial salt such as sodium sulfate and sodium chloride is high, the product value is low, the market demand is small, and the zero emission treatment of pollutants is challenged. At present, the more researched physicochemical treatment methods of high-salinity wastewater mainly comprise the following steps: evaporation, coagulating sedimentation, electrolysis and membrane separation.
The evaporation method has the function of removing salt and organic pollutants in the wastewater. Although the method for reducing the volume of pollutant emission by evaporating and concentrating the high-salinity wastewater by using natural conditions is economically feasible, certain requirements are made on local natural conditions and the quality of the wastewater.
The coagulation method cannot effectively remove soluble salts in the high-salinity wastewater, but can effectively remove colloidal COD in the high-salinity wastewater and simultaneously reduce the turbidity of the wastewater, and is commonly used as a pretreatment process of the high-salinity wastewater.
The principle of treating waste water by electrolysis method is mainly characterized by that it utilizes the action of external current to produce a series of physical and chemical reactions to reduce toxic harmful substances in the waste water, and the organic substances in the waste water can produce electrode redox reaction on the positive and negative electrodes to produce water-insoluble substances, and then the water-insoluble substances can be precipitated (or floated) or directly oxidized and reduced into harmless gas to remove them so as to reduce COD. Among them, bipolar membrane Electrodialysis (EDBM) has been explored as a bipolar membrane, which is a novel ion exchange membrane, and is composed of an anion exchange layer, a cation exchange layer and an intermediate layer. The water molecules of the middle catalyst layer of the bipolar membrane generate water dissociation reaction to generate H+And OH-Under the driving action of reverse voltage on two sides of the bipolar membrane, H+And OH-Respectively permeate into the solution main body through the cation exchange layer and the anion exchange layer, and the water dissociation balance of the middle layer is broken, so that the bipolar membrane hydrolysis process is continuously carried out. Bipolar membrane water splitting can provide H by means of electrodialysis in contrast to conventional electrolysis of water+And OH-Without generating by-product H2And O2Thus reducing energy consumption. However, the hardness of the inlet water cannot meet the requirements of the bipolar membrane, and the membrane can be blocked, so that the electrolysis device is greatly influenced.
Therefore, there is a need for a sustainable recycling economy solution that truly "renewables" from wastewater, and for economic reasons and environmental protection, can recover water and other acid and base products that are more valuable than industrial salts from high salinity wastewater.
Disclosure of Invention
The invention aims to solve the problem of discharge of industrial wastewater containing high-concentration salt and heavy metal, combines a reverse osmosis device and a bipolar membrane electrodialysis device, and arranges an induced crystallization device and an ion exchange resin device between the two devices, thereby not only obtaining high water yield and saving water resources, but also removing hard ions and heavy metal ions in the wastewater, reducing the risk of membrane blockage, generating acid and alkali byproducts with high value, and solving the problem of low value of byproduct crystalline salt and limited market demand.
The invention provides a system for recycling and treating high-salt industrial wastewater resources, which comprises a reverse osmosis device and a bipolar membrane electrodialysis device, wherein an induced crystallization device is arranged between the reverse osmosis device and the bipolar membrane electrodialysis device;
the induced crystallization device comprises a body, a water inlet, a medicine feeding port, a crystallized particle discharging port, a seed crystal feeding port and a water outlet, wherein the water inlet, the medicine feeding port and the crystallized particle discharging port are arranged at the bottom of the body; the medicine adding port is used for adding NaOH or Na2CO3(ii) a The water inlet is connected with the water production port of the reverse osmosis device, the water outlet is connected with the bipolar membrane electrodialysis device, and the effluent of the induced crystallization device is used as the liquid inlet of the bipolar membrane electrodialysis device;
the reverse osmosis device is used for concentrating the incoming water, the bipolar membrane electrodialysis device is used for hydrolyzing and ionizing water molecules to form recoverable acid and alkali, and the induced crystallization device is used for removing heavy metal ions and/or Ca of the concentrated incoming water2+So as to meet the liquid inlet requirement of the bipolar membrane electrodialysis device.
According to the high-salt industrial wastewater resource recovery treatment system, as a preferred mode, a second reverse osmosis device is further arranged between the induced crystallization device and the bipolar membrane electrodialysis device, a water outlet is connected with a water inlet of the second reverse osmosis device, a water outlet of the second reverse osmosis device is connected with a liquid inlet of the bipolar membrane electrodialysis device, and water outlet of the second reverse osmosis device is used as liquid inlet of the bipolar membrane electrodialysis device.
According to the high-salt industrial wastewater resource recycling and treating system, as a preferred mode, a water tank is arranged between a second reverse osmosis device and a bipolar membrane electrodialysis device, a water inlet of the water tank is connected with a water outlet of the second reverse osmosis device, a first water outlet of the water tank is connected with a water inlet of the reverse osmosis device, a second water outlet of the water tank is connected with a liquid inlet of the bipolar membrane electrodialysis device, and water outlet of the second water outlet of the water tank is used as liquid inlet of the bipolar membrane electrodialysis device.
According to the high-salt industrial wastewater resource recovery treatment system, as a preferable mode, the liquid inlet end of the bipolar membrane electrodialysis device is further provided with an ion exchange resin device, anion exchange resin and cation exchange resin are respectively arranged in the ion exchange resin device, and the ion exchange resin device is used for removing anions and cations in an ion form of liquid inlet.
The invention relates to a high-salt industrial wastewater resource recovery treatment system, which is characterized in that as a preferred mode, a bipolar membrane electrodialysis device is of a bipolar membrane electrodialysis membrane stack structure and comprises a cathode electrode, an anode electrode, a bipolar membrane electrodialysis membrane stack, a partition plate, an acid chamber and an alkali chamber, wherein the cathode electrode and the anode electrode are positioned on two sides of the bipolar membrane electrodialysis device; the bipolar membrane electrodialysis membrane stack comprises an anode membrane, a cathode membrane and bipolar membranes which are sequentially arranged, an independent anode membrane is further arranged between the bipolar membrane electrodialysis membrane stack and an anode electrode, the number of the bipolar membrane electrodialysis membrane stacks is not less than 2, a partition plate is used for separating the bipolar membrane electrodialysis membrane stack, acid liquor is generated between the cathode membrane and the bipolar membranes and flows into an acid chamber, alkali liquor is generated between the bipolar membranes and the anode membrane and flows into an alkali chamber, and water is discharged outside.
The high-salt industrial wastewater resource recovery treatment system is preferably provided with 3 bipolar membrane electrodialysis membrane stacks.
The invention provides a method for recycling and treating high-salt industrial wastewater resources, which comprises the following steps:
s1, feeding incoming water into a reverse osmosis device for concentration to obtain concentrated incoming water;
s2, concentrated incoming water enters an induced crystallization device and is added into NaOH or Na2CO3Under the action of (2) heavy metal ions and/or Ca2 +Generating water-insoluble heavy metal salt or carbonate in an induced crystallization mode and discharging the water-insoluble heavy metal salt or carbonate out of an induced crystallization device to obtain a first feed liquor;
and S3, enabling the first liquid inlet to enter a bipolar membrane electrodialysis device, generating acid and alkali under the action of a cathode electrode, an anode electrode and a bipolar membrane electrodialysis membrane stack, conveying the acid and the alkali to an acid chamber and an alkali chamber, obtaining recyclable acid liquid and alkali liquid, and discharging produced water.
The invention provides a method for recycling and treating high-salt industrial wastewater resources, which comprises the following steps:
s1, feeding incoming water into a reverse osmosis device for concentration to obtain concentrated incoming water;
s2, concentrated incoming water enters an induced crystallization device and is added into NaOH or Na2CO3Under the action of (2), heavy metal ions and/or Ca2+Generating water-insoluble heavy metal salt or carbonate in an induced crystallization mode and discharging the water-insoluble heavy metal salt or carbonate out of an induced crystallization device to obtain a first feed liquor;
s2', the first feed liquid enters a second reverse osmosis device to be continuously concentrated to obtain a second feed liquid;
and S3', the second liquid enters a bipolar membrane electrodialysis device, acid and alkali are generated under the action of a cathode electrode, an anode electrode and a bipolar membrane electrodialysis membrane stack and are conveyed to an acid chamber and an alkali chamber, recyclable acid liquid and recyclable alkali liquid are obtained, and produced water is discharged outside.
The invention provides a method for recycling and treating high-salt industrial wastewater resources, which comprises the following steps:
s1, feeding incoming water into a reverse osmosis device for concentration to obtain concentrated incoming water;
s2, concentrated incoming water enters an induced crystallization device and is added into NaOH or Na2CO3Under the action of (2), heavy metal ions and/or Ca2+Generating water-insoluble heavy metal salt or carbonate in an induced crystallization mode and discharging the water-insoluble heavy metal salt or carbonate out of an induced crystallization device to obtain a first feed liquor; (ii) a
S2'. feeding the first feed liquor into a second reverse osmosis device to be continuously concentrated to obtain a second feed liquor, feeding the second feed liquor into a water tank, and when the effluent Ca of the water tank is2+When the concentration is higher than 50mg/L, the water is discharged from the first water outlet and continuously enters a reverse osmosis device, an induced crystallization device and a second reverse osmosis device for concentration and heavy metal ion and/or Ca removal2+Up to the outlet Ca of the tank2+At a concentration of less than 50mg/L, the second step isDischarging the liquid from a water outlet to obtain third liquid inlet;
and S3'. the third feed liquid enters a bipolar membrane electrodialysis device, acid and alkali are generated under the action of a cathode electrode, an anode electrode and a bipolar membrane electrodialysis membrane stack and are conveyed to an acid chamber and an alkali chamber, so that recyclable acid liquid and alkali liquid are obtained, and the produced water is discharged outside.
According to the method for recycling and treating the high-salt industrial wastewater resource, the first inlet liquid in the step S3, the second inlet liquid in the step S3 'and the third inlet liquid in the step S3' are preferably fed into an ion exchange resin device to remove anions and cations in ionic forms, and then fed into a bipolar membrane electrodialysis device.
The incoming water is concentrated by a reverse osmosis device, enters an induced crystallization device to remove hard ions and heavy metal ions in the wastewater, and NaOH or Na is added2CO3Formation of calcium carbonate and insoluble heavy metal bases or carbonates, e.g. Ni (OH)2、NiCO3And the effluent of the induced crystallization device is first feed liquor, the first feed liquor enters a second reverse osmosis device for continuous concentration to obtain second feed liquor, and the second feed liquor enters a water tank and then continues to enter the reverse osmosis device, the induced crystallization device and the second reverse osmosis device for concentration and heavy metal ion and/or Ca removal2+Water Ca up to the water tank2+And when the concentration is lower than 50mg/L, namely the effluent hardness meets the bipolar membrane water inlet condition, obtaining a third feed liquid.
The invention utilizes the bipolar membrane and other anion and cation exchange membranes to form an electrodialysis system, and under the condition of not introducing new components, the electrodialysis system and salts in the wastewater are converted to generate corresponding acid and alkali.
The bipolar membrane electrodialysis device adopts a bipolar membrane electrodialysis membrane stack structure and consists of three parts: (1) cathode and anode, titanium ruthenium-coated electrode material, and direct current power supply is connected with (2) cathode membrane (FAB), anode membrane (FKB) and bipolar membrane (FBM); (3) the baffle, organic glass material, thickness 1cm, the size is according to membrane stack size adjustment. With Na+And SO4 2-As an example of the concentrate as the main component, 0.5M Na2SO4The solution is used as an electrode washing liquid. Under an applied electric field, anions (Cl)-And SO4 2-) Move across the FAB membrane, while cations (Na, K, Sr, Ca, Ni, etc.) cross the FKB membrane. Meanwhile, hydroxide ions and protons are generated from the FBM membrane and transported to the base compartment and the acid compartment, respectively. Since sodium and sodium sulfate are mainly present in the pretreated wastewater in which multivalent cations are removed by inducing crystallization in the crystallization fluidized bed reactor, sulfuric acid and sodium hydroxide are used as the initial solutions, respectively, in order to make the acid and alkali sufficient. The feasibility of generating acid and alkali by pretreating wastewater is tested by adopting a bipolar membrane electrodialysis method. The current efficiency of the acid can be as high as 69%, and the current efficiency of the base can be as high as 80%. At 60mA/cm2The energy consumption was 5.5kWh/kg acid and 4.8kW h/kg base at the current density of (1).
The invention utilizes chemical induced crystallization granulation as a pretreatment process to remove hard ions (Ca, Mg) and heavy metals (Fe, Mn, Co, Ni and the like, but not limited to the hard ions and the heavy metals, as long as all metal ions of hydroxide which is difficult to dissolve in water can be formed) in high-salinity water, effluent enters bipolar membrane electrodialysis, and Na which is abundantly existed in water is introduced+，Cl-Or SO42-Generating alkali (NaOH) and acid (HCl or H) after the bipolar membrane electrodialysis treatment2SO4) The alkali and the acid are recycled and used for the front-end pretreatment acid-base dosing procedure. The produced water can be directly discharged.
The invention can be used for treating various heavy metal-containing high-salt industrial wastewater, including RO (single-stage or multi-stage) concentrated water, NF concentrated water advanced treatment and resource recycling. The water yield can also be improved by matching induced crystallization with multi-stage RO, the induced crystallization hardness removal device is positioned between two sets of reverse osmosis membrane stacks, the RO1 concentrated water enters the hardness removal device, and the outlet water is taken as RO2And (4) water is fed. And (3) further softening the periodically discharged concentrated solution by using ion exchange resin, and recycling the acid and alkali corresponding to salt ions in the concentrated water by using bipolar membrane electrodialysis.
The invention has the following advantages:
(1) aiming at the high-salt concentrated water, particularly the high-salt concentrated water containing heavy metals, acid and alkali byproducts with high values can be generated during desalination treatment and directly reused in a water treatment system or other production procedures, and the problem that the byproduct crystalline salt has low value and limited market demand is solved.
(2) When no induced crystallization pretreatment is carried out before bipolar membrane electrodialysis, scaling on a cation exchange membrane can reduce alkali regeneration performance, hard ions and heavy metal ions in concentrated water can be removed through induced crystallization, and impurities which can cause membrane fouling and blocking such as partial silicon dioxide and organic matters are taken away through coprecipitation.
(3) The high water yield is obtained by using common RO under the condition of low pressure control, the yield is over 90 percent, no water-containing sludge is generated, the fouling and blocking probability of an RO membrane is greatly reduced, and the running is stable under higher osmotic pressure;
(4) aiming at the problem that high-salt concentrated water, especially heavy-metal-containing high-salt concentrated water, can generate acid and alkali byproducts with high values during desalination treatment, can be directly reused in a water treatment system or other production procedures, and solves the problem that the byproduct crystalline salt has low value and limited market demand.
(5) Ion exchange resin is used for pretreatment before bipolar membrane electrodialysis, so that the concentration of impurity ions is reduced, the scaling probability on a cation exchange membrane is reduced, and the alkali regeneration performance is improved.
Drawings
FIG. 1 is a schematic diagram of a high salt industrial wastewater resource recovery processing system and method in an embodiment 1;
FIG. 2 is a structural diagram of a high-salt industrial wastewater resource recovery treatment system and method induced crystallization device;
FIG. 3 is a schematic diagram of a high salt industrial wastewater resource recovery processing system and method in the embodiment 2;
FIG. 4 is a schematic diagram of a high salt industrial wastewater resource recovery processing system and method in the embodiment 3;
FIG. 5 is a diagram of the construction of an embodiment 4 of a high salt industrial wastewater resource recovery processing system and method;
FIG. 6 is a structural diagram of a bipolar membrane electrodialysis device for the resource recovery treatment system and method of high-salt industrial wastewater;
FIG. 7 is a schematic diagram of a high salt industrial wastewater resource recovery processing system and method in accordance with example 6;
FIG. 8 is a schematic diagram of an embodiment 7 of a high salt industrial wastewater resource recovery processing system and method;
FIG. 9 is a flow chart of an embodiment 8 of the system and method for recycling and treating high-salt industrial wastewater resources;
FIG. 10 is a flow chart of an embodiment 9 of a high-salt industrial wastewater resource recovery processing system and method;
FIG. 11 is a flow chart of an embodiment 10 of a high salt industrial wastewater resource recovery processing system and method;
FIG. 12 is a flow chart of an embodiment 11 of a high salt industrial wastewater resource recovery processing system and method;
FIG. 13 is a flow chart of an embodiment 12 of a high salt industrial wastewater resource recovery processing system and method;
FIG. 14 is a flow chart of an embodiment 13 of a high-salt industrial wastewater resource recovery processing system and method.
Reference numerals:
1. a reverse osmosis unit; 2. a bipolar membrane electrodialysis device; 21. a cathode electrode; 22. an anode electrode; 23. a bipolar membrane electrodialysis membrane stack; 231. a positive membrane; 232. a negative film; 233. bipolar membrane; 24. a partition plate; 25. an acid chamber; 26. an alkali chamber; 27. a single sun membrane; 3. an induced crystallization device; 31. a body; 32. a water inlet; 33. a medicine adding port; 34. a crystalline particle discharge port; 35. a seed crystal feeding port; 36. a water outlet; 4. a second reverse osmosis unit; 5. a water tank; 6. ion exchange resin device.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
As shown in fig. 1, a high-salt industrial wastewater resource recovery treatment system comprises a reverse osmosis device 1 and a bipolar membrane electrodialysis device 2, wherein an induced crystallization device 3 is arranged between the reverse osmosis device 1 and the bipolar membrane electrodialysis device 2;
the reverse osmosis device 1 is used for concentrating incoming water;
the bipolar membrane electrodialysis device 2 is used for hydrolyzing and ionizing water molecules to form recoverable acid and alkali;
as shown in fig. 2, the induced crystallization device 3 comprises a body 31, a water inlet 32, a drug feeding port 33, a crystallized particle discharging port 34 arranged at the bottom of the body 31, a seed crystal feeding port 35 arranged at one side of the top of the body 31, and a water outlet 36 arranged at the opposite side of the top of the body 31 to the seed crystal feeding port 35; the medicine adding port 33 is used for adding NaOH or Na2CO3(ii) a The water inlet 32 is connected with a water producing port of the reverse osmosis device 1, the water outlet 36 is connected with the bipolar membrane electrodialysis device 2, and the water outlet of the induced crystallization device 3 is used as the liquid inlet of the bipolar membrane electrodialysis device 2; the induced crystallization device 3 is used for removing heavy metal ions and/or Ca in the concentrated incoming water2+So as to meet the liquid inlet requirement of the bipolar membrane electrodialysis device 2.
Example 2
As shown in fig. 3, a high-salt industrial wastewater resource recycling treatment system comprises a reverse osmosis device 1 and a bipolar membrane electrodialysis device 2, wherein an induced crystallization device 3 is arranged between the reverse osmosis device 1 and the bipolar membrane electrodialysis device 2, and a second reverse osmosis device 4 is also arranged between the induced crystallization device 3 and the bipolar membrane electrodialysis device 2;
the reverse osmosis device 1 is used for concentrating incoming water;
the bipolar membrane electrodialysis device 2 is used for hydrolyzing and ionizing water molecules to form recoverable acid and alkali;
the induced crystallization device 3 comprises a body 31, a water inlet 32, a medicine feeding port 33, a crystallized particle discharging port 34, a seed crystal putting port 35 and a water outlet 36, wherein the water inlet 32, the medicine feeding port 33 and the crystallized particle discharging port 34 are arranged at the bottom of the body 31; the medicine adding port 33 is used for adding NaOH or Na2CO3(ii) a The water inlet 32 is connected with a water producing port of the reverse osmosis device 1, and the water outlet 36 is connected with a water inlet of the second reverse osmosis device 4; the induced crystallization device 3 is used for removing heavy metal ions and/or Ca in the concentrated incoming water2+So as to meet the liquid inlet requirement of the bipolar membrane electrodialysis device 2;
the water outlet of the second reverse osmosis device 4 is connected with the liquid inlet of the bipolar membrane electrodialysis device 2, and the water outlet of the second reverse osmosis device 4 is used as the liquid inlet of the bipolar membrane electrodialysis device 2;
example 3
As shown in fig. 4, a high-salt industrial wastewater resource recycling treatment system comprises a reverse osmosis device 1 and a bipolar membrane electrodialysis device 2, wherein an induced crystallization device 3 is arranged between the reverse osmosis device 1 and the bipolar membrane electrodialysis device 2, a second reverse osmosis device 4 is further arranged between the induced crystallization device 3 and the bipolar membrane electrodialysis device 2, and a water tank 5 is arranged between the second reverse osmosis device 4 and the bipolar membrane electrodialysis device 2;
the reverse osmosis device 1 is used for concentrating incoming water;
the bipolar membrane electrodialysis device 2 is used for hydrolyzing and ionizing water molecules to form recoverable acid and alkali;
the induced crystallization device 3 comprises a body 31, a water inlet 32, a medicine feeding port 33, a crystallized particle discharging port 34, a seed crystal putting port 35 and a water outlet 36, wherein the water inlet 32, the medicine feeding port 33 and the crystallized particle discharging port 34 are arranged at the bottom of the body 31; the medicine adding port 33 is used for adding NaOH or Na2CO3(ii) a The water inlet 32 is connected with a water producing port of the reverse osmosis device 1, and the water outlet 36 is connected with a water inlet of the second reverse osmosis device 4; the induced crystallization device 3 is used for removing heavy metal ions and/or Ca in the concentrated incoming water2+So as to meet the liquid inlet requirement of the bipolar membrane electrodialysis device 2;
the water inlet of the water tank 5 is connected with the water outlet of the second reverse osmosis device 4, the first water outlet of the water tank 5 is connected with the water inlet of the reverse osmosis device 1, the second water outlet of the water tank 5 is connected with the liquid inlet of the bipolar membrane electrodialysis device 2, and the outlet water of the second water outlet of the water tank 5 is used as the liquid inlet of the bipolar membrane electrodialysis device 2.
Example 4
As shown in fig. 5, a high-salt industrial wastewater resource recovery treatment system comprises a reverse osmosis device 1 and a bipolar membrane electrodialysis device 2, wherein an induced crystallization device 3 is arranged between the reverse osmosis device 1 and the bipolar membrane electrodialysis device 2, and an ion exchange resin device 6 is further arranged at a liquid inlet end of the bipolar membrane electrodialysis device 2;
the reverse osmosis device 1 is used for concentrating incoming water;
the bipolar membrane electrodialysis device 2 is used for hydrolyzing and ionizing water molecules to form recoverable acid and alkali;
the induced crystallization device 3 comprises a body 31, a water inlet 32, a medicine feeding port 33, a crystallized particle discharging port 34, a seed crystal putting port 35 and a water outlet 36, wherein the water inlet 32, the medicine feeding port 33 and the crystallized particle discharging port 34 are arranged at the bottom of the body 31; the medicine adding port 33 is used for adding NaOH or Na2CO3(ii) a The water inlet 32 is connected with a water producing port of the reverse osmosis device 1, the water outlet 36 is connected with the bipolar membrane electrodialysis device 2, and the effluent of the water outlet 36 is used as the inlet liquid of the bipolar membrane electrodialysis device 2; the induced crystallization device 3 is used for removing heavy metal ions and/or Ca in the concentrated incoming water2+So as to meet the liquid inlet requirement of the bipolar membrane electrodialysis device 2;
the ion exchange resin device 6 is provided with an anion exchange resin and a cation exchange resin, respectively, and the ion exchange resin device 6 is used for removing anions and cations in an ionic form from the feed liquid.
Example 5
As shown in fig. 1, a high-salt industrial wastewater resource recovery treatment system comprises a reverse osmosis device 1 and a bipolar membrane electrodialysis device 2, wherein an induced crystallization device 3 is arranged between the reverse osmosis device 1 and the bipolar membrane electrodialysis device 2;
the reverse osmosis device 1 is used for concentrating incoming water;
as shown in fig. 6, the bipolar membrane electrodialysis device 2 is used to hydrolyze and ionize water molecules, forming recoverable acids and bases; the bipolar membrane electrodialysis device 2 is a bipolar membrane electrodialysis membrane stack structure and comprises a cathode 21, an anode 22, a bipolar membrane electrodialysis membrane stack 23, a partition plate 24, an acid chamber 25 and an alkali chamber 26, wherein the cathode 21 and the anode 22 are positioned on two sides of the bipolar membrane electrodialysis device 2; the bipolar membrane electrodialysis membrane stack 23 comprises an anode membrane 231, a cathode membrane 232 and bipolar membranes 233 which are sequentially arranged, a single anode membrane 27 is further arranged between the bipolar membrane electrodialysis membrane stack 23 and the anode 22, the number of the bipolar membrane electrodialysis membrane stacks 23 is not less than 2, the partition plate 24 is used for separating the bipolar membrane electrodialysis membrane stacks 23, acid liquor is generated between the cathode membrane 232 and the bipolar membranes 233 and flows into the acid chamber 25, alkali liquor is generated between the bipolar membranes 233 and the anode membrane 231 and flows into the alkali chamber 26, and produced water is discharged; the bipolar membrane electrodialysis device 2 is used for hydrolyzing and ionizing water molecules to form recoverable acid and alkali;
the induced crystallization device 3 comprises a body 31, a water inlet 32, a medicine feeding port 33, a crystallized particle discharging port 34, a seed crystal putting port 35 and a water outlet 36, wherein the water inlet 32, the medicine feeding port 33 and the crystallized particle discharging port 34 are arranged at the bottom of the body 31; the medicine adding port 33 is used for adding NaOH or Na2CO3(ii) a The water inlet 32 is connected with a water producing port of the reverse osmosis device 1, the water outlet 36 is connected with the bipolar membrane electrodialysis device 2, and the effluent of the water outlet 36 is used as the inlet liquid of the bipolar membrane electrodialysis device 2; the induced crystallization device 3 is used for removing heavy metal ions and/or Ca in the concentrated incoming water2+So as to meet the liquid inlet requirement of the bipolar membrane electrodialysis device 2.
Example 6
As shown in FIG. 7, the number of the bipolar membrane electrodialysis membrane stacks 23 is preferably 3 on the basis of example 6.
Example 7
As shown in fig. 8, a high-salt industrial wastewater resource recycling treatment system comprises a reverse osmosis device 1 and a bipolar membrane electrodialysis device 2, wherein an induced crystallization device 3 is arranged between the reverse osmosis device 1 and the bipolar membrane electrodialysis device 2, a second reverse osmosis device 4 is further arranged between the induced crystallization device 3 and the bipolar membrane electrodialysis device 2, a water tank 5 is arranged between the second reverse osmosis device 4 and the bipolar membrane electrodialysis device 2, and an ion exchange resin device 6 is further arranged at a liquid inlet end of the bipolar membrane electrodialysis device 2;
the reverse osmosis device 1 is used for concentrating incoming water;
the bipolar membrane electrodialysis device 2 is used for hydrolyzing and ionizing water molecules to form recoverable acid and alkali; the bipolar membrane electrodialysis device 2 is a bipolar membrane electrodialysis membrane stack structure and comprises a cathode 21, an anode 22, a bipolar membrane electrodialysis membrane stack 23, a partition plate 24, an acid chamber 25 and an alkali chamber 26, wherein the cathode 21 and the anode 22 are positioned on two sides of the bipolar membrane electrodialysis device 2; the bipolar membrane electrodialysis membrane stack 23 comprises an anode membrane 231, a cathode membrane 232 and bipolar membranes 233 which are sequentially arranged, a single anode membrane 27 is further arranged between the bipolar membrane electrodialysis membrane stack 23 and the anode 22, the number of the bipolar membrane electrodialysis membrane stacks 23 is not less than 2, the partition plate 24 is used for separating the bipolar membrane electrodialysis membrane stacks 23, acid liquor is generated between the cathode membrane 232 and the bipolar membranes 233 and flows into the acid chamber 25, alkali liquor is generated between the bipolar membranes 233 and the anode membrane 231 and flows into the alkali chamber 26, and produced water is discharged; the bipolar membrane electrodialysis device 2 is used for hydrolyzing and ionizing water molecules to form recoverable acid and alkali;
the induced crystallization device 3 is used for removing heavy metal ions and/or Ca in the concentrated incoming water2+So as to meet the water inlet requirement of the bipolar membrane electrodialysis device 2; the induced crystallization device 3 comprises a body 31, a water inlet 32, a medicine feeding port 33, a crystallized particle discharging port 34, a seed crystal putting port 35 and a water outlet 36, wherein the water inlet 32, the medicine feeding port 33 and the crystallized particle discharging port 34 are arranged at the bottom of the body 31; the medicine adding port 33 is used for adding NaOH or Na2CO3(ii) a The water inlet 32 is connected with a water producing port of the reverse osmosis device 1, and the water outlet 36 is connected with a water inlet of the second reverse osmosis device 4; the induced crystallization device 3 is used for removing heavy metal ions and/or Ca in the concentrated incoming water2+So as to meet the liquid inlet requirement of the bipolar membrane electrodialysis device 2;
a water inlet of the water tank 5 is connected with a water outlet of the second reverse osmosis device 4, a first water outlet of the water tank 5 is connected with a water inlet of the reverse osmosis device 1, and a second water outlet of the water tank 5 is connected with a liquid inlet of the ion exchange resin device 6;
the liquid outlet of the ion exchange resin device 6 is connected with the liquid inlet of the bipolar membrane electrodialysis device, the ion exchange resin device 6 is respectively provided with anion exchange resin and cation exchange resin, and the ion exchange resin device 6 is used for removing anions and cations in the form of ions in the liquid inlet.
The use method of the embodiment comprises the following steps:
the incoming water is concentrated by a reverse osmosis device, enters an induced crystallization device to remove hard ions and heavy metal ions in the wastewater, and NaOH or Na is added2CO3Formation of calcium carbonate and insoluble heavy metal bases or carbonates, e.g. Ni (OH)2、NiCO3And the effluent of the induced crystallization device is first feed liquor, the first feed liquor enters a second reverse osmosis device to be continuously concentrated to obtain second feed liquor,the second feed liquid enters the water tank and then continues to enter the reverse osmosis device, the induced crystallization device and the second reverse osmosis device for concentration and heavy metal ion and/or Ca removal2+Water Ca up to the water tank2+And when the concentration is lower than 50mg/L, namely the effluent hardness meets the bipolar membrane water inlet condition, obtaining a third feed liquid.
The invention utilizes the bipolar membrane and other anion and cation exchange membranes to form an electrodialysis system, and under the condition of not introducing new components, the electrodialysis system and salts in the wastewater are converted to generate corresponding acid and alkali.
The bipolar membrane electrodialysis device adopts a bipolar membrane electrodialysis membrane stack structure and consists of three parts: (1) cathode and anode, titanium ruthenium-coated electrode material, and direct current power supply is connected with (2) cathode membrane (FAB), anode membrane (FKB) and bipolar membrane (FBM); (3) the baffle, organic glass material, thickness 1cm, the size is according to membrane stack size adjustment. With Na+And SO4 2-As an example of the concentrate as the main component, 0.5M Na2SO4The solution is used as an electrode washing liquid. Under an applied electric field, anions (Cl)-And SO4 2-) Move across the FAB membrane, while cations (Na, K, Sr, Ca, Ni, etc.) cross the FKB membrane. Meanwhile, hydroxide ions and protons are generated from the FBM membrane and transported to the base compartment and the acid compartment, respectively. Since sodium and sodium sulfate are mainly present in the pretreated wastewater in which multivalent cations are removed by inducing crystallization in the crystallization fluidized bed reactor, sulfuric acid and sodium hydroxide are used as the initial solutions, respectively, in order to make the acid and alkali sufficient. The feasibility of generating acid and alkali by pretreating wastewater is tested by adopting a bipolar membrane electrodialysis method. The current efficiency of the acid can be as high as 69%, and the current efficiency of the base can be as high as 80%. At 60mA/cm2The energy consumption was 5.5kWh/kg acid and 4.8kW h/kg base at the current density of (1).
The invention utilizes chemical induced crystallization granulation as a pretreatment process to remove hard ions (Ca, Mg) and heavy metals (Fe, Mn, Co, Ni and the like, but not limited to the hard ions and the heavy metals, as long as all metal ions of hydroxide which is difficult to dissolve in water can be formed) in high-salinity water, effluent enters bipolar membrane electrodialysis, and Na which is abundantly existed in water is introduced+，Cl-Or SO42-JingshuangAlkali (NaOH) and acid (HCl or H) are generated after the polar membrane electrodialysis treatment2SO4) The alkali and the acid are recycled and used for the front-end pretreatment acid-base dosing procedure. The produced water can be directly discharged.
The invention can be used for treating various heavy metal-containing high-salt industrial wastewater, including RO (single-stage or multi-stage) concentrated water, NF concentrated water advanced treatment and resource recycling. The water yield can also be improved by matching induced crystallization with multi-stage RO, the induced crystallization hardness removal device is positioned between two sets of reverse osmosis membrane stacks, the RO1 concentrated water enters the hardness removal device, and the outlet water is taken as RO2And (4) water is fed. And (3) further softening the periodically discharged concentrated solution by using ion exchange resin, and recycling the acid and alkali corresponding to salt ions in the concentrated water by using bipolar membrane electrodialysis.
Example 8
As shown in fig. 9, a method for recycling and treating high-salinity industrial wastewater resource includes the following steps:
s1, feeding the incoming water into a reverse osmosis device 1 for concentration to obtain concentrated incoming water;
s2, concentrated incoming water enters an induced crystallization device 3 and is added into NaOH or Na2CO3Under the action of (2) heavy metal ions and/or Ca2+Generating water-insoluble heavy metal salt or carbonate in an induced crystallization mode and discharging the water-insoluble heavy metal salt or carbonate out of the induced crystallization device 3 to obtain a first feed liquid;
s3, enabling the first liquid inlet to enter a bipolar membrane electrodialysis device 2, generating acid and alkali under the action of a cathode electrode 21, an anode electrode 22 and a bipolar membrane electrodialysis membrane stack 23, conveying the acid and the alkali to an acid chamber 25 and an alkali chamber 26, obtaining recyclable acid liquid and recyclable alkali liquid, and discharging produced water.
Example 9
As shown in fig. 10, a method for recycling and treating high-salinity industrial wastewater resource includes the following steps:
s1, feeding the incoming water into a reverse osmosis device 1 for concentration to obtain concentrated incoming water;
s2, concentrated incoming water enters an induced crystallization device 3 and is added into NaOH or Na2CO3Under the action of (2) heavy metal ions and/or Ca2+Generating water-insoluble heavy metal salt or carbonate by induced crystallization and discharging the induced crystallizationA device 3 for obtaining a first feed liquid;
s2', the first feed liquid enters a second reverse osmosis device 4 for continuous concentration to obtain a second feed liquid;
and S3', enabling the second liquid to enter the bipolar membrane electrodialysis device 2, generating acid and alkali under the action of the cathode electrode 21, the anode electrode 22 and the bipolar membrane electrodialysis membrane stack 23, conveying the acid and the alkali to the acid chamber 25 and the alkali chamber 26, obtaining recyclable acid liquid and alkali liquid, and discharging the produced water.
Example 10
As shown in fig. 11, a method for recycling and treating high-salinity industrial wastewater resource includes the following steps:
s1, feeding the incoming water into a reverse osmosis device 1 for concentration to obtain concentrated incoming water;
s2, concentrated incoming water enters an induced crystallization device 3 and is added into NaOH or Na2CO3Under the action of (2) heavy metal ions and/or Ca2+Generating water-insoluble heavy metal salt or carbonate in an induced crystallization mode and discharging the water-insoluble heavy metal salt or carbonate out of the induced crystallization device 3 to obtain a first feed liquid;
s2' when the first feed liquid enters the second reverse osmosis device 4 to be continuously concentrated to obtain the second feed liquid, the second feed liquid enters the water tank 5, and when the effluent Ca of the water tank 52+When the concentration is higher than 50mg/L, the water is discharged from the first water outlet and continuously enters the reverse osmosis device 1, the induced crystallization device 3 and the second reverse osmosis device 4 for concentration and heavy metal ion and/or Ca removal2+Up to the outlet Ca of the tank 52+When the concentration is lower than 50mg/L, discharging from a second water outlet to obtain a third inlet liquid;
and S3, feeding the third feed liquid into the bipolar membrane electrodialysis device 2, generating acid and alkali under the action of the cathode electrode 21, the anode electrode 22 and the bipolar membrane electrodialysis membrane stack 23, conveying the acid and alkali to the acid chamber 25 and the alkali chamber 26, obtaining recyclable acid liquid and alkali liquid, and discharging the produced water.
Example 11
As shown in fig. 12, a method for recycling and treating high-salinity industrial wastewater resource includes the following steps:
s1, feeding the incoming water into a reverse osmosis device 1 for concentration to obtain concentrated incoming water;
s2, concentrated incoming water entersAn apparatus for inducing crystallization 3 in NaOH or Na2CO3Under the action of (2) heavy metal ions and/or Ca2+Generating water-insoluble heavy metal salt or carbonate in an induced crystallization mode and discharging the water-insoluble heavy metal salt or carbonate out of the induced crystallization device 3 to obtain a first feed liquid;
s3, enabling the first feed liquid to enter an ion exchange resin device 6 to remove anions and cations in an ionic form, then enabling the first feed liquid to enter a bipolar membrane electrodialysis device 2, generating acid and alkali under the action of a cathode electrode 21, an anode electrode 22 and a bipolar membrane electrodialysis membrane stack 23, conveying the acid and alkali to an acid chamber 25 and an alkali chamber 26, obtaining recyclable acid liquid and alkali liquid, and discharging produced water.
Example 12
As shown in fig. 13, a method for recycling and treating high-salinity industrial wastewater resource includes the following steps:
s1, feeding the incoming water into a reverse osmosis device 1 for concentration to obtain concentrated incoming water;
s2, concentrated incoming water enters an induced crystallization device 3 and is added into NaOH or Na2CO3Under the action of (2) heavy metal ions and/or Ca2+Generating water-insoluble heavy metal salt or carbonate in an induced crystallization mode and discharging the water-insoluble heavy metal salt or carbonate out of the induced crystallization device 3 to obtain a first feed liquid;
s2', the first feed liquid enters a second reverse osmosis device 4 for continuous concentration to obtain a second feed liquid;
and S3', the second feed liquid enters an ion exchange resin device 6 to remove anions and cations in ionic forms, then enters a bipolar membrane electrodialysis device 2, generates acid and alkali under the action of a cathode electrode 21, an anode electrode 22 and a bipolar membrane electrodialysis membrane stack 23, and conveys the acid and alkali to an acid chamber 25 and an alkali chamber 26 to obtain recyclable acid liquid and alkali liquid, and the produced water is discharged outside.
Example 13
As shown in fig. 14, a method for recycling and treating high-salinity industrial wastewater resource includes the following steps:
s1, feeding the incoming water into a reverse osmosis device 1 for concentration to obtain concentrated incoming water;
s2, concentrated incoming water enters an induced crystallization device 3 and is added into NaOH or Na2CO3Under the action of (2) heavy metal ions and/or Ca2+Generating water-insoluble heavy metal salt or carbonate in an induced crystallization mode and discharging the water-insoluble heavy metal salt or carbonate out of the induced crystallization device 3 to obtain a first feed liquid; (ii) a
S2' when the first feed liquid enters the second reverse osmosis device 4 to be continuously concentrated to obtain the second feed liquid, the second feed liquid enters the water tank 5, and when the effluent Ca of the water tank 52+When the concentration is higher than 50mg/L, the water is discharged from the first water outlet and continuously enters the reverse osmosis device 1, the induced crystallization device 3 and the second reverse osmosis device 4 for concentration and heavy metal ion and/or Ca removal2+Up to the outlet Ca of the tank 52+When the concentration is lower than 50mg/L, discharging from a second water outlet to obtain a third inlet liquid;
and S3, enabling the third feed liquid to enter an ion exchange resin device 6 to remove anions and cations in ionic forms, then entering a bipolar membrane electrodialysis device 2, generating acid and alkali under the action of a cathode electrode 21, an anode electrode 22 and a bipolar membrane electrodialysis membrane stack 23, conveying the acid and alkali to an acid chamber 25 and an alkali chamber 26, obtaining recyclable acid liquid and alkali liquid, and discharging produced water.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (10)

1. The utility model provides a high salt industrial waste water resource recovery processing system, includes reverse osmosis unit (1) and bipolar membrane electrodialysis device (2), its characterized in that: an induced crystallization device (3) is arranged between the reverse osmosis device (1) and the bipolar membrane electrodialysis device (2);
the induced crystallization device (3) comprises a body (31), a water inlet (32), a dosing port (33) and a crystallized particle discharge port (34) which are arranged at the bottom of the body (31), a seed crystal putting port (35) which is arranged at one side of the top of the body (31) and a water outlet (36) which is arranged at one side of the top of the body (31) opposite to the seed crystal putting port (35); the medicine adding port (33) is used for adding NaOH or Na2CO3(ii) a The water inlet (32) and the reverse osmosis deviceConnecting a water producing port (1) with a liquid inlet of the bipolar membrane electrodialysis device (2), and using the outlet water of the induced crystallization device (3) as the liquid inlet of the bipolar membrane electrodialysis device (2);
the reverse osmosis device (1) is used for concentrating incoming water, the bipolar membrane electrodialysis device (2) is used for hydrolyzing and ionizing water molecules to form recoverable acid and alkali, and the induced crystallization device (3) is used for removing heavy metal ions and/or Ca of the concentrated incoming water2+So as to meet the liquid inlet requirement of the bipolar membrane electrodialysis device (2).
2. The high-salt industrial wastewater resource recovery and treatment system according to claim 1, characterized in that: a second reverse osmosis device (4) is further arranged between the induced crystallization device (3) and the bipolar membrane electrodialysis device (2), the water outlet (36) is connected with the water inlet of the second reverse osmosis device (4), the water outlet of the second reverse osmosis device (4) is connected with the liquid inlet of the bipolar membrane electrodialysis device (2), and the outlet water of the second reverse osmosis device (4) is used as the liquid inlet of the bipolar membrane electrodialysis device (2).
3. The high-salt industrial wastewater resource recovery and treatment system according to claim 2, characterized in that: the second reverse osmosis device (4) with be provided with water tank (5) between bipolar membrane electrodialysis device (2), the water inlet of water tank (5) with the delivery port of second reverse osmosis device (4) links to each other, the first delivery port of water tank (5) with the water inlet of reverse osmosis device (1) links to each other, the second delivery port of water tank (5) with the inlet of bipolar membrane electrodialysis device (2) links to each other, the play water of the second delivery port of water tank (5) is used as the feed liquor of bipolar membrane electrodialysis device (2).
4. The high-salt industrial wastewater resource recovery and treatment system according to claim 1, characterized in that: an ion exchange resin device (6) is further arranged at the liquid inlet end of the bipolar membrane electrodialysis device (2), anion exchange resin and cation exchange resin are respectively arranged in the ion exchange resin device (6), and the ion exchange resin device (6) is used for removing anions and cations in the form of ions in the liquid inlet.
5. The high-salt industrial wastewater resource recovery and treatment system according to claim 1, characterized in that: the bipolar membrane electrodialysis device (2) is of a bipolar membrane electrodialysis membrane stack structure and comprises a negative electrode (21), a positive electrode (22), a bipolar membrane electrodialysis membrane stack (23), a partition plate (24), an acid chamber (25) and an alkali chamber (26), wherein the negative electrode (21) and the positive electrode (22) are positioned on two sides of the bipolar membrane electrodialysis device (2); the bipolar membrane electrodialysis membrane stack (23) comprises an anode membrane (231), a cathode membrane (232) and a bipolar membrane (233) which are sequentially arranged, the bipolar membrane electrodialysis membrane stack (23) and an independent anode membrane (27) are further arranged between the anode electrodes (22), the number of the bipolar membrane electrodialysis membrane stack (23) is not less than 2, the partition board (24) is used for separating the bipolar membrane electrodialysis membrane stack (23), acid liquor is generated between the cathode membrane (232) and the bipolar membrane (233) and flows into the acid chamber (25), alkali liquor is generated between the bipolar membrane (233) and the anode membrane (231) and flows into the alkali chamber (26), and the generated water is discharged outside.
6. The high-salt industrial wastewater resource recovery and treatment system according to claim 5, characterized in that: the number of the bipolar membrane electrodialysis membrane stacks (23) is 3.
7. A high-salt industrial wastewater resource recovery treatment method comprises the following steps:
s1, feeding the incoming water into a reverse osmosis device (1) for concentration to obtain concentrated incoming water;
s2, the concentrated incoming water enters an induced crystallization device (3) and is subjected to reaction with NaOH or Na2CO3Under the action of (2) heavy metal ions and/or Ca2+Generating water-insoluble heavy metal salt or carbonate in an induced crystallization mode, and discharging the water-insoluble heavy metal salt or carbonate out of the induced crystallization device (3) to obtain a first feed liquid;
and S3, the first liquid inlet enters a bipolar membrane electrodialysis device (2), acid and alkali are generated under the action of a cathode electrode (21), an anode electrode (22) and a bipolar membrane electrodialysis membrane stack (23) and are conveyed to an acid chamber (27) and an alkali chamber (28), recyclable acid liquid and recyclable alkali liquid are obtained, and produced water is discharged outside.
8. A high-salt industrial wastewater resource recovery processing method is characterized in that: the method comprises the following steps:
s1, feeding the incoming water into a reverse osmosis device (1) for concentration to obtain concentrated incoming water;
s2, the concentrated incoming water enters the induced crystallization device (3) and is subjected to reaction in NaOH or Na2CO3Under the action of (2) heavy metal ions and/or Ca2+Generating water-insoluble heavy metal salt or carbonate in an induced crystallization mode, discharging the water-insoluble heavy metal salt or carbonate out of the induced crystallization device (3) and discharging the water-insoluble heavy metal salt or carbonate out of the induced crystallization device (3) to obtain a first feed liquid;
s2', the first feed liquid enters a second reverse osmosis device (4) to be continuously concentrated to obtain second feed liquid;
and S3', the second feed liquid enters the bipolar membrane electrodialysis device (2), acid and alkali are generated under the action of the cathode electrode (21), the anode electrode (22) and the bipolar membrane electrodialysis membrane stack (23) and are conveyed to the acid chamber (27) and the alkali chamber (28), and recyclable acid liquid and alkali liquid are obtained and discharged.
9. A high-salt industrial wastewater resource recovery processing method is characterized in that: the method comprises the following steps:
s1, feeding the incoming water into a reverse osmosis device (1) for concentration to obtain concentrated incoming water;
s2, the concentrated incoming water enters the induced crystallization device (3) and is subjected to reaction in NaOH or Na2CO3Under the action of (2), heavy metal ions and/or Ca2+Generating water-insoluble heavy metal salt or carbonate in an induced crystallization mode, discharging the water-insoluble heavy metal salt or carbonate out of the induced crystallization device (3) and discharging the water-insoluble heavy metal salt or carbonate out of the induced crystallization device (3) to obtain a first feed liquid;
s2'. the first feed liquid enters the second reverse osmosis device (4) to be continuously concentrated to obtain a second feed liquid, the second feed liquid enters the water tank (5), and when the outlet Ca of the water tank (5) is concentrated, the second feed liquid enters the water tank (5)2+When the concentration is higher than 50mg/L,is discharged from the first water outlet and continuously enters the reverse osmosis device (1), the induced crystallization device (3) and the second reverse osmosis device (4) for concentration and heavy metal ion and/or Ca removal2+Until the water outlet Ca of the water tank (5)2+When the concentration is lower than 50mg/L, discharging from a second water outlet to obtain a third inlet liquid;
and S3', the third feed liquid enters the bipolar membrane electrodialysis device (2), and acid and alkali are generated under the action of the cathode electrode (21), the anode electrode (22) and the bipolar membrane electrodialysis membrane stack (23) and are conveyed to the acid chamber (27) and the alkali chamber (28), so that recyclable acid liquid and alkali liquid are obtained, and produced water is discharged.
10. The method for recycling and treating the high-salinity industrial wastewater resource according to the claims 7 to 9, characterized in that: the first feed liquid in the step S3, the second feed liquid in the step S3 'and the third feed liquid in the step S3' enter an ion exchange resin device (6) to remove anions and cations in an ionic form and then enter the bipolar membrane electrodialysis device (2).
CN202010603205.4A 2020-06-29 2020-06-29 High-salt industrial wastewater resource recovery treatment system and method Pending CN111675394A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112551791A (en) * 2020-12-04 2021-03-26 北京朗新明环保科技有限公司 Zero-emission method for treating negative hard mine water by crystallization granulation softening coupling membrane method
CN113526760A (en) * 2021-05-24 2021-10-22 国能朗新明环保科技有限公司 Recycling treatment system and method for efficient reuse of salt-containing mine water
CN115849524A (en) * 2023-02-23 2023-03-28 西安泰瑞环保技术有限公司 Method, device and equipment for recovering heavy metals in wastewater based on improved electrodialysis method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112551791A (en) * 2020-12-04 2021-03-26 北京朗新明环保科技有限公司 Zero-emission method for treating negative hard mine water by crystallization granulation softening coupling membrane method
CN113526760A (en) * 2021-05-24 2021-10-22 国能朗新明环保科技有限公司 Recycling treatment system and method for efficient reuse of salt-containing mine water
CN115849524A (en) * 2023-02-23 2023-03-28 西安泰瑞环保技术有限公司 Method, device and equipment for recovering heavy metals in wastewater based on improved electrodialysis method

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