CN113003806A - Method and device for separating monovalent ions and multivalent ions in water - Google Patents
Method and device for separating monovalent ions and multivalent ions in water Download PDFInfo
- Publication number
- CN113003806A CN113003806A CN202110280669.0A CN202110280669A CN113003806A CN 113003806 A CN113003806 A CN 113003806A CN 202110280669 A CN202110280669 A CN 202110280669A CN 113003806 A CN113003806 A CN 113003806A
- Authority
- CN
- China
- Prior art keywords
- water
- ions
- membrane
- monovalent
- concentrated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 289
- 150000002500 ions Chemical class 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000012528 membrane Substances 0.000 claims abstract description 124
- 150000001450 anions Chemical class 0.000 claims abstract description 72
- 238000001728 nano-filtration Methods 0.000 claims abstract description 60
- 238000000909 electrodialysis Methods 0.000 claims abstract description 59
- 150000001768 cations Chemical class 0.000 claims abstract description 57
- 239000013505 freshwater Substances 0.000 claims abstract description 56
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 33
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 239000012466 permeate Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 26
- -1 chlorine ions Chemical class 0.000 description 42
- 229910001414 potassium ion Inorganic materials 0.000 description 24
- 229910001415 sodium ion Inorganic materials 0.000 description 24
- 230000005684 electric field Effects 0.000 description 18
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 14
- 229910001425 magnesium ion Inorganic materials 0.000 description 14
- 229910002651 NO3 Inorganic materials 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 9
- 229910001424 calcium ion Inorganic materials 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000002893 slag Substances 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 239000012267 brine Substances 0.000 description 6
- 230000000149 penetrating effect Effects 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- XZPVPNZTYPUODG-UHFFFAOYSA-M sodium;chloride;dihydrate Chemical compound O.O.[Na+].[Cl-] XZPVPNZTYPUODG-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
- C02F2101/101—Sulfur 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
- C02F2101/12—Halogens or halogen-containing 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method and a device for separating monovalent ions and multivalent ions in water, wherein the method comprises the following steps: s1, introducing water to be treated into a container with an electrodialysis membrane for electrodialysis, wherein the water to be treated is divided into fresh water and first concentrated water by the electrodialysis membrane; s2, performing nanofiltration on the fresh water to generate produced water and second concentrated water; s3, performing reverse osmosis concentration on the produced water to form third concentrated water, and performing electrodialysis on the third concentrated water, or directly performing electrodialysis on the produced water to form second produced water and first concentrated water. The device comprises a fresh water chamber and a concentrated water chamber, wherein the fresh water chamber and the concentrated water chamber are separated by an electrodialysis membrane; the electrodialysis membranes include at least one pair of cation membranes and monovalent anion permselective membranes. The invention solves the problem of the prior concentrated salt moisture and salt treatment: the method has the practical problems that the chloride ions of the concentrated water recycled after the nanofiltration salt separation exceed the standard and the like.
Description
Technical Field
The invention relates to the technical field of salt separation, in particular to a method and a device for separating monovalent ions and multivalent ions in water.
Background
In industrial production, a large amount of high-quality water resources are needed, and mainly circulating cooling water is used. Because a large amount of water is evaporated in the process of circulating cooling water, salt, organic matters and the like in the water are concentrated. Therefore, no matter what treatment, separation or concentration method is adopted, part of water is finally higher in salt content than the inlet water, namely higher in salt content than the local underground water or surface water. If the part of the concentrated brine water is directly discharged, the local water quality is obviously affected, and the consequences of salinization, aquatic organism death, water ecological damage and the like are caused. Therefore, the scientific and reasonable disposal method is usually only achieved by changing the excessive salt into solid phase to achieve the integral balance of salt. Several methods are reasonable, one is to evaporate and crystallize the high-content salt water to prepare salt; one is to concentrate and reduce the amount of high salt-containing water for reuse and absorption. The problem that a large amount of mixed salt is produced at the end of salt preparation by evaporation and crystallization to become dangerous waste so that the subsequent treatment cost is greatly increased is solved, pure salt is prepared from a purer part after salt separation, and the mixed salt is treated by other methods.
The mainstream salt separation mode in the market at present is to directly use a nanofiltration membrane. The principle of the nanofiltration membrane is that pressure is used as driving force, monovalent ions in water are forced to permeate the nanofiltration membrane along with water to form water, and most of multivalent ions cannot permeate the nanofiltration membrane to be intercepted and are discharged along with concentrated water of the nanofiltration membrane. In the process of nanofiltration separation of salt, monovalent ions such as chloride ions and the like have no additional separation driving force, so that the concentration of the monovalent ions in nanofiltration concentrated water is not obviously reduced compared with nanofiltration inlet water, and only the concentration of multivalent ions is increased. The salt separation mode can not meet the actual requirements of enterprises in some times, for example, nanofiltration concentrated water after salt separation is used for hot disintegration of steel slag in a steel mill, the water specification of hot disintegration of the steel slag for new removal of the steel slag makes a regulation on the water quality of the water for disintegrating slag, and the water for disintegrating slag in various concentrated brine treatment processes in the current market mainly contains chloride ions exceeding the 1000mg/L limit value specified in the technical specification of water for hot disintegration of steel slag, so that the problem that the water is not in accordance with the regulation exists. And when the chlorine ions of the inlet water subjected to nanofiltration exceed 1000mg/L, the concentrated water cannot effectively reduce the content of the chlorine ions, and the problem that the chlorine ions exceed the standard when the concentrated brine is used for hot disintegration of steel slag cannot be solved.
In addition, there is a less frequently used salt separation technique, namely monovalent anion permselective electrodialysis. The principle of monovalent anion permselective electrodialysis is: the anion in the fresh water chamber moves towards the anode direction by taking the electric field as a driving force, monovalent anion can permeate the membrane to enter the concentrated water chamber when meeting a monovalent anion selective membrane, and multivalent ion is intercepted by the monovalent ion selective membrane and is remained in the fresh water chamber, so that the effect of separating monovalent anion from multivalent anion is achieved.
Disclosure of Invention
The invention aims to provide a method and a device for separating monovalent ions and multivalent ions in water, which are used for solving at least one technical problem and can solve one problem of the prior brine-brine separation treatment: the method has the practical problems that the chloride ions of the concentrated water recycled after the nanofiltration salt separation exceed the standard and the like.
The embodiment of the invention is realized by the following steps:
in a first aspect, embodiments of the present invention provide a method for separating monovalent ions from multivalent ions in water, including:
s1, introducing water to be treated into a container with an electrodialysis membrane for electrodialysis, wherein the water to be treated is divided into fresh water and first concentrated water by the electrodialysis membrane.
S2, performing nanofiltration on the fresh water to generate produced water and second concentrated water.
S3, performing reverse osmosis concentration on the produced water to form third concentrated water, performing electrodialysis on the third concentrated water, or directly performing electrodialysis on the produced water to form second produced water and first concentrated water, and storing divalent anions in the second concentrated water in the nanofiltration zone.
In combination with the first aspect, the present examples provide a first possible implementation manner of the first aspect, wherein, in S1, the electrodialysis membrane includes at least one pair of a cation membrane and a monovalent anion permselective membrane.
The cation membrane and the monovalent anion permselective membrane are disposed between the electrodes.
In combination with the first aspect, the present invention provides a second possible implementation manner of the first aspect, wherein the cation membrane and the monovalent anion permselective membrane are sequentially assembled in pairs, so as to separate the water to be treated into a plurality of fresh water chambers and a plurality of concentrated water chambers.
In combination with the first aspect, the present examples provide a third possible implementation manner of the first aspect, wherein, in S1, the water to be treated is separated into fresh water and first concentrated water by the electrodialysis membrane, wherein the formation of the fresh water comprises:
monovalent anions (chloride ions and nitrate ions) move to the positively charged electrode by the driving force of the electric field, permeate through the monovalent anion permselective membrane, and reach the concentrated water chamber.
The polyvalent anions (sulfate ions) move to the positively charged electrode due to the driving force of the electric field, and most of the polyvalent anions cannot permeate through the monovalent anion permselective membrane and are trapped in the dilute chamber.
When the cation membrane is a non-permselective membrane, cations (sodium ions, potassium ions, magnesium ions, and the like) move to the negatively charged electrode due to the driving force of the electric field, and reach the concentrate chamber after penetrating through the cation membrane. When the cation membrane adopts a monovalent cation permselective membrane, monovalent cations (sodium ions, potassium ions, ammonium ions and the like) move to the negatively charged electrode due to the driving force of an electric field and reach the concentrated water chamber after penetrating through the cation membrane; multivalent cations (magnesium ions, calcium ions, iron ions, etc.) move to the negatively charged electrode due to the driving force of the electric field, and most of the multivalent cations cannot permeate through the monovalent cation permselective membrane and are trapped in the dilute chamber.
And a plurality of fresh water chambers are communicated to form fresh water outlet water, the contents of monovalent anions (chloride ions) and monovalent cations (sodium ions and potassium ions) in the fresh water outlet water are lower than that of the water to be treated, and the contents of polyvalent anions (sulfate radicals, phosphate radicals and the like) are not lower than that of the water to be treated.
In combination with the first aspect, the present invention provides a fourth possible implementation manner of the first aspect, wherein, in S1, the water to be treated is separated into fresh water and first concentrated water by the electrodialysis membrane, and the first concentrated water is formed by a process including:
monovalent anions (chloride ions, nitrate ions) and polyvalent anions (sulfate ions) move toward the positively charged electrode due to the driving force of the electric field, are trapped by the cation membrane in the moving direction, and are trapped in the concentrated water chamber.
When the cation membrane is a non-permselective membrane, cations (sodium ions, potassium ions, magnesium ions, and the like) move to the negatively charged electrode due to the driving force of the electric field, and reach the concentrate chamber after penetrating through the cation membrane. When the cation membrane adopts a monovalent cation permselective membrane, monovalent cations (sodium ions, potassium ions, ammonium ions and the like) move to the negatively charged electrode due to the driving force of an electric field and reach the concentrated water chamber after penetrating through the cation membrane; multivalent cations (magnesium ions, calcium ions, iron ions, etc.) move to the negatively charged electrode due to the driving force of the electric field, and most of the multivalent cations cannot permeate through the monovalent cation permselective membrane and are trapped in the dilute chamber.
And the multiple concentrated water chambers are communicated to form a first concentrated water outlet, and the content of monovalent anions (chloride ions) and cations (sodium ions and potassium ions) in the first concentrated water outlet is higher than that of the water to be treated.
With reference to the first aspect, an embodiment of the present invention provides a fifth possible implementation manner of the first aspect, where in S2, the nanofiltration process includes:
and the fresh water enters a nanofiltration treatment facility. In the separation process, water, various ions, organic matters and the like in the inlet water are extruded towards the direction of the nanofiltration membrane under the driving of pressure, water can greatly permeate the electrodialysis membrane to reach a water production side due to the selective permeability of the nanofiltration membrane and the interception characteristic of the membrane, monovalent ions such as sodium ions, potassium ions, chloride ions, nitrate ions and the like can greatly permeate the nanofiltration membrane to reach a concentrated water side, most polyvalent ions such as sulfate ions, calcium ions, magnesium ions and the like are intercepted at the concentrated water side due to the selective permeability of the nanofiltration membrane, and most pollutants such as organic matters and the like are intercepted at the concentrated water side due to the interception characteristic of the nanofiltration membrane. Therefore, after the treatment of the nanofiltration membrane, compared with the inlet water, the produced water on the water production side has reduced organic matters, greatly reduced polyvalent ions such as sulfate radicals, calcium ions, magnesium ions and the like, and no large change in monovalent ions such as sodium ions, potassium ions, chloride ions, nitrate ions and the like; compared with the inlet water, monovalent ions such as sodium ions, potassium ions, chloride ions, nitrate ions and the like of the second concentrated water on the concentrated water side do not change greatly or are reduced slightly, and because a large amount of water reaches the fresh water side, the water quantity on the concentrated water side is reduced, the content of organic matters on the concentrated water side is increased, and the content of multivalent ions such as sulfate radicals, calcium ions, magnesium ions and the like is increased.
In combination with the first aspect, the present invention provides a sixth possible implementation manner of the first aspect, in S3, after the water produced after nanofiltration is concentrated by reverse osmosis, the reverse-osmosis third concentrated water is returned to the device with the electrodialysis membrane 3, the second produced water can be used as industrial fresh water, desalted water, etc., the content of organic matters and various ions in the reverse-osmosis second produced water is greatly reduced compared with the first produced water, and the content of organic matters and various ions in the reverse-osmosis third concentrated water is increased compared with the first produced water due to the reduction of the water amount.
The treatment effect of the whole process is as follows: one strand of monovalent ion concentrated water (first concentrated water) is produced from a concentrated water chamber of a container provided with an electrodialysis membrane, one strand of multivalent ion concentrated water (second concentrated water) is produced from a concentrated water side of nanofiltration, and when a reverse osmosis membrane is arranged, one strand of reverse osmosis produced water (second produced water) is produced from a reverse osmosis produced water side. Compared with the feed water, the monovalent ion concentrated water (first concentrated water) has greatly reduced polyvalent anions such as sulfate radical, and increased monovalent ion contents such as sodium ion, potassium ion, chloride ion, and nitrate radical ion. Compared with the inlet water, the multivalent ion concentrated water (second concentrated water) has the advantages that the content of monovalent ions such as sodium ions, potassium ions, chloride ions, nitrate ions and the like is reduced, the content of organic matters is increased, and the content of multivalent anions such as sulfate radicals and the like is increased. Compared with the inlet water, the organic matters and various ions in the reverse osmosis water (second water) are greatly reduced.
In a second aspect, the embodiments of the present invention further provide a separation device for monovalent ions and multivalent ions, which includes a dilute water chamber and a concentrated water chamber, wherein the dilute water chamber and the concentrated water chamber are separated by an electrodialysis membrane.
The electrodialysis membranes include at least one pair of cation membranes and monovalent anion permselective membranes.
In combination with the second aspect, the present invention provides a first possible implementation manner of the second aspect, wherein the cation membrane and the monovalent anion permselective membrane are sequentially assembled in pairs to form a stack, and the separation device is divided into a plurality of fresh water chambers and a plurality of concentrated water chambers.
With reference to the second aspect, an embodiment of the present invention provides a second possible implementation manner of the second aspect, where the apparatus further includes a nanofiltration device, and after the fresh water chambers are communicated, the nanofiltration device is connected to an inlet end of the nanofiltration device.
With reference to the second aspect, the embodiment of the present invention provides a third possible implementation manner of the second aspect, wherein the third possible implementation manner further includes a reverse osmosis device, and after the plurality of concentrated water chambers are communicated, the water outlet end of the reverse osmosis device is connected.
The water inlet end of the reverse osmosis device is connected with the water outlet end of the nanofiltration device.
The embodiment of the invention has the beneficial effects that:
the invention provides a method and a device for separating monovalent ions and multivalent ions in water, which solve the problem of processing the water and the salt of concentrated salt at present: the method has the practical problems that the chloride ions of the concentrated water recycled after the nanofiltration salt separation exceed the standard and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic structural diagram of an apparatus for separating monovalent ions from multivalent ions in water according to the present invention;
FIG. 2 is a schematic flow chart of the method for separating monovalent ions from multivalent ions in water according to the present invention;
FIG. 3 is a schematic flow chart of another method for separating monovalent ions from multivalent ions in water according to the present invention.
In the figure: 1-a fresh water chamber; 2-concentrated water chamber; 3-electrodialysis membranes; 4-a nanofiltration device; 5-reverse osmosis device.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, 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 some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein can be arranged and designed in a wide variety of different configurations.
Some embodiments of the invention are described in detail below with reference to the accompanying drawings. The embodiments described below and the features of the embodiments can be combined with each other without conflict.
Referring to fig. 1 to 3, a first embodiment of the present invention provides a method for separating monovalent ions from multivalent ions in water, comprising:
s1, introducing water to be treated into a container with an electrodialysis membrane 3 for electrodialysis, wherein the water to be treated is divided into fresh water and first concentrated water by the electrodialysis membrane 3.
S2, performing nanofiltration on the fresh water to generate produced water and second concentrated water.
S3, performing reverse osmosis concentration on the produced water to form third concentrated water, performing electrodialysis on the third concentrated water, or directly performing electrodialysis on the produced water to form second produced water and first concentrated water, and storing divalent anions in the second concentrated water in the nanofiltration zone.
In combination with the first aspect, the present embodiments provide a first possible implementation manner of the first aspect, wherein, in S1, the electrodialysis membrane 3 includes at least one pair of a cation membrane and a monovalent anion permselective membrane.
The cation membrane and the monovalent anion permselective membrane are disposed between the electrodes.
In combination with the first aspect, the present invention provides a second possible implementation manner of the first aspect, wherein the cation membrane and the monovalent anion permselective membrane are sequentially assembled in pairs, so as to separate the water to be treated into a plurality of fresh water chambers 1 and a plurality of concentrated water chambers 2.
In combination with the first aspect, the present embodiments provide a third possible implementation manner of the first aspect, wherein, in S1, the water to be treated is separated into fresh water and first concentrated water by the electrodialysis membrane 3, wherein the formation process of the fresh water includes:
monovalent anions (chloride ions and nitrate ions) move to the positively charged electrode by the driving force of the electric field, permeate through the monovalent anion permselective membrane, and reach the concentrated water chamber 2.
The polyvalent anions (sulfate ions) move to the positively charged electrode by the driving force of the electric field, and most of them cannot permeate the monovalent anion permselective membrane and are trapped in the dilute chamber 1. Specifically, approximately 90% of the polyvalent anion is impermeable to the monovalent anion permselective membrane.
Cations (sodium ions, potassium ions, and magnesium ions) move to the negatively charged electrode due to the driving force of the electric field, and reach the concentrated water chamber 2 after penetrating or partially penetrating the cation membrane. Specifically, when the cation membrane is a non-selectively permeable membrane, cations (sodium ions, potassium ions, magnesium ions, and the like) move to the negatively charged electrode due to the driving force of the electric field, and reach the concentrate chamber after permeating the cation membrane in a proportion of about 95%. When the cation membrane is a monovalent cation permselective membrane, monovalent cations (sodium ions, potassium ions, ammonium ions and the like) move to the negatively charged electrode due to the driving force of an electric field, and approximately 95% of the monovalent cations penetrate through the cation membrane and then reach a concentrated water chamber; multivalent cations (magnesium ions, calcium ions, iron ions, etc.) migrate to the negatively charged electrode due to the driving force of the electric field, and are approximately 90% of the monovalent cation permselective membrane that cannot permeate through the membrane and are trapped in the dilute chamber.
The fresh water chambers 1 are communicated to form fresh water outlet water, the content of monovalent anions (chloride ions) and cations (sodium ions and potassium ions) in the fresh water outlet water is lower than that of the water to be treated, and the content of polyvalent anions (sulfate radicals, phosphate radicals and the like) is equivalent to that of the water to be treated or the concentration of the polyvalent anions is slightly higher than about 10%.
In combination with the first aspect, the present invention provides a fourth possible implementation manner of the first aspect, wherein, in S1, the water to be treated is separated into fresh water and first concentrated water by the electrodialysis membrane 3, and the first concentrated water is formed by a process including:
monovalent anions (chloride ions) and polyvalent anions (sulfate, phosphate, etc.) move to the positively charged electrode due to the driving force of the electric field, are trapped by the cation membrane in the moving direction, and are trapped in the concentrate chamber 2.
Cations (sodium ions, potassium ions and magnesium ions) move to the negatively charged electrode due to the driving force of the electric field, are trapped by the monovalent anions in the moving direction through the ion membrane, and are trapped in the concentrated water chamber 2.
And the concentrated water chambers 2 are communicated to form a first concentrated water outlet, and the content of monovalent anions (chloride ions) and cations (sodium ions and potassium ions) in the first concentrated water outlet is higher than that of the water to be treated.
With reference to the first aspect, an embodiment of the present invention provides a fifth possible implementation manner of the first aspect, where in S2, the nanofiltration process includes:
and the fresh water enters a nanofiltration treatment facility. In the separation process, water, various ions, organic matters and the like in the inlet water are extruded towards the direction of the nanofiltration membrane under the driving of pressure, water can greatly permeate the electrodialysis membrane to reach a water production side due to the selective permeability of the nanofiltration membrane and the interception characteristic of the membrane, monovalent ions such as sodium ions, potassium ions, chloride ions, nitrate ions and the like can greatly permeate the nanofiltration membrane to reach a concentrated water side, most polyvalent ions such as sulfate ions, calcium ions, magnesium ions and the like are intercepted at the concentrated water side due to the selective permeability of the nanofiltration membrane, and most pollutants such as organic matters and the like are intercepted at the concentrated water side due to the interception characteristic of the nanofiltration membrane. Therefore, after the treatment of the nanofiltration membrane, compared with the inlet water, the produced water on the water production side has reduced organic matters, greatly reduced polyvalent ions such as sulfate radicals, calcium ions, magnesium ions and the like, and no large change in monovalent ions such as sodium ions, potassium ions, chloride ions, nitrate ions and the like; compared with the inlet water, monovalent ions such as sodium ions, potassium ions, chloride ions, nitrate ions and the like of the second concentrated water on the concentrated water side do not change greatly or are reduced slightly, and because a large amount of water reaches the fresh water side, the water quantity on the concentrated water side is reduced, the content of organic matters on the concentrated water side is increased, and the content of multivalent ions such as sulfate radicals, calcium ions, magnesium ions and the like is increased.
In combination with the first aspect, the present invention provides a sixth possible implementation manner of the first aspect, in S3, after the water produced after nanofiltration is concentrated by reverse osmosis, the reverse-osmosis third concentrated water is returned to the device with the electrodialysis membrane 3, the second produced water can be used as industrial fresh water, desalted water, etc., the content of organic matters and various ions in the reverse-osmosis second produced water is greatly reduced compared with the first produced water, and the content of organic matters and various ions in the reverse-osmosis second concentrated water is increased compared with the first produced water due to the reduction of the water amount.
The treatment effect of the whole process is as follows: one strand of monovalent ion concentrated water (first concentrated water) is produced from a concentrated water chamber 2 of a container provided with an electrodialysis membrane 3, one strand of multivalent ion concentrated water (second concentrated water) is produced from a concentrated water side of nanofiltration, and when a reverse osmosis membrane is arranged, one strand of reverse osmosis produced water (second produced water) is produced from a reverse osmosis produced water side. Compared with the feed water, the monovalent ion concentrated water (first concentrated water) has greatly reduced polyvalent anions such as sulfate radical, and increased monovalent ion contents such as sodium ion, potassium ion, chloride ion, and nitrate radical ion. Compared with the inlet water, the multivalent ion concentrated water (second concentrated water) has the advantages that the content of monovalent ions such as sodium ions, potassium ions, chloride ions, nitrate ions and the like is reduced, the content of organic matters is increased, and the content of multivalent anions such as sulfate radicals and the like is increased. Compared with the inlet water, the organic matters and various ions in the reverse osmosis water (second water) are greatly reduced.
Referring to fig. 1, a second embodiment of the present invention provides a separation device for monovalent ions and multivalent ions, comprising a dilute water chamber 1 and a concentrated water chamber 2, wherein the dilute water chamber 1 and the concentrated water chamber 2 are separated by an electrodialysis membrane 3.
The electrodialysis membrane 3 comprises at least one pair of a cation membrane and a monovalent anion permselective membrane.
In combination with the second aspect, the present invention provides a first possible implementation manner of the second aspect, wherein the cation membrane and the monovalent anion permselective membrane are sequentially assembled in pairs to form a stack, and the separation device is divided into a plurality of fresh water chambers 1 and a plurality of concentrated water chambers 2.
With reference to the second aspect, the embodiment of the present invention provides a second possible implementation manner of the second aspect, wherein a nanofiltration device 4 is further included, and after the plurality of fresh water chambers 1 are communicated, the fresh water chambers are connected to an inlet end of the nanofiltration device.
With reference to the second aspect, the embodiment of the present invention provides a third possible implementation manner of the second aspect, wherein the third possible implementation manner further includes a reverse osmosis device 5, and after the plurality of concentrated water chambers 2 are communicated, the third possible implementation manner is connected to a water outlet end of the reverse osmosis device.
Referring to fig. 2, a third embodiment of the present invention provides a process for separating monovalent ions and multivalent ions in water, comprising:
(1) wastewater subjected to pretreatment for removing hardness and advanced oxidation for removing COD enters a three-stage monovalent anion permselective electrodialysis device.
(2) Fresh water of the monovalent anion permselective electrodialysis device enters the wide-flow-channel anti-pollution nanofiltration device 4, and concentrated water of the monovalent anion permselective electrodialysis device receives chloride ions, sodium ions and potassium ions from the fresh water chamber to form relatively pure monovalent ion concentrated brine which is subjected to subsequent evaporation crystallization treatment.
(3) The produced water of the anti-pollution nanofiltration device 4 enters a reverse osmosis device; the concentrated water of the nanofiltration device 4 is sent to a subsequent resin adsorption method to remove COD and then sent to a steel slag hot closed process for digestion.
(4) The concentrated water of the reverse osmosis device 5 enters a monovalent anion permselective electrodialysis device.
The relevant water quality is shown in table 1.
Table 1: example 3 Water quality Table (Steel works high-concentration brine treatment project)
| Item | Unit of | Inflow water | Electrodialytic fresh water | Nanofiltration concentrated water | Nanofiltration water production | Reverse osmosis concentrated water | Reverse osmosis water production | Electrodialysis concentrated water |
| Designed water quantity | m3/h | 27 | 27 | 8 | 19 | 6 | 13 | 6 |
| TDS | mg/L | 51580 | 12998 | 36996 | 2713 | 8400 | 68 | 182019 |
| pH | - | 7 | 7 | 7 | 7 | 8 | 7 | 8 |
| Na | mg/L | 18183 | 937 | 902 | 952 | 2956 | 20 | 80563 |
| K | mg/L | 190 | 8 | 8 | 8 | 25 | 0 | 844 |
| Ca | mg/ |
2 | 2 | 7 | 0 | 0 | 0 | 0 |
| Mg | mg/ |
1 | 1 | 3 | 0 | 0 | 0 | 0 |
| NH4 | mg/L | 7 | 2 | 2 | 2 | 4 | 1 | 27 |
| CL | mg/L | 22125 | 986 | 951 | 1001 | 3104 | 23 | 98229 |
| SO4 | mg/L | 10847 | 10989 | 35053 | 676 | 2084 | 21 | 1445 |
| HCO3 | mg/L | 60 | 3 | 3 | 3 | 7 | 1 | 264 |
| NO3 | mg/L | 163 | 69 | 67 | 70 | 216 | 2 | 639 |
| F | mg/ |
2 | 1 | 1 | 1 | 3 | 0 | 8 |
| SiO2 | mg/L | 33 | 33 | 108 | 1 | 3 | 0 | 3 |
| COD | mg/L | 82 | 80 | 234 | 14 | 40 | 2 | 49 |
Referring to fig. 3, a fourth embodiment of the present invention provides a process for separating monovalent ions and multivalent ions in water, comprising:
(1) the wastewater after pretreatment and hardness removal enters a monovalent anion permselective electrodialysis device.
(2) Fresh water of the monovalent anion permselective electrodialysis device enters the nanofiltration device 4, concentrated water of the monovalent anion permselective electrodialysis device receives chloride ions, sodium ions and potassium ions from the fresh water chamber to form relatively pure monovalent ion concentrated brine, and the bipolar membrane acid and alkali preparation is carried out after the monovalent anion permselective electrodialysis device carries out subsequent electrodialysis concentration treatment.
(3) The water produced by the nanofiltration device 4 enters a monovalent anion permselective electrodialysis device.
The relevant water quality is shown in table 2.
Table 2 water quality table of each step of example 4
| Item | Unit of | Inflow water | Monovalent anion selective electrodialysis of fresh water | Nanofiltration concentrated water | Nanofiltration water production | Monovalent anion selective electrodialysis concentrated water |
| Designed water quantity | m3/h | 50 | 50 | 16 | 34 | 34 |
| TDS | mg/L | 40191 | 16502 | 32877 | 8796 | 43633 |
| pH | - | 7.8 | 7.6 | 7.0 | 7.3 | 7.9 |
| Na | mg/L | 14266 | 3855 | 3738 | 3910 | 19220 |
| K | mg/L | 35 | 22 | 20 | 23 | 42 |
| Ca | mg/L | 12 | 8 | 25 | 0 | 6 |
| Mg | mg/L | 10 | 5 | 16 | 0 | 7 |
| NH4 | mg/ |
3 | 2 | 2 | 2 | 3 |
| CL | mg/L | 17612 | 4646 | 4561 | 4686 | 23754 |
| SO4 | mg/L | 8028 | 7897 | 24453 | 106 | 299 |
| HCO3 | mg/L | 99 | 36 | 34 | 37 | 130 |
| NO3 | mg/L | 126 | 31 | 29 | 32 | 172 |
| F | mg/L | 0 | 0 | 0 | 0 | 0 |
| SiO2 | mg/L | 13 | 13 | 41 | 0 | 0 |
| COD | mg/L | 122 | 120 | 350 | 12 | 15 |
The embodiment of the invention aims at protecting and separating monovalent ions and multivalent ions in water, and has the following effects:
the invention provides a method and a device for separating monovalent ions and multivalent ions in water, which solve the problem of processing the water and the salt of concentrated salt at present: the method has the practical problems that the chloride ions of the concentrated water recycled after the nanofiltration salt separation exceed the standard and the like.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (9)
1. A method for separating monovalent ions from multivalent ions in water, comprising:
s1, introducing water to be treated into a container with an electrodialysis membrane (3) for electrodialysis, wherein the water to be treated is divided into fresh water and first concentrated water by the electrodialysis membrane (3);
s2, performing nanofiltration on the fresh water to generate produced water and second concentrated water;
s3, performing reverse osmosis concentration on the produced water to form third concentrated water, and performing electrodialysis on the third concentrated water, or directly performing electrodialysis on the produced water to form second produced water and first concentrated water.
2. The method for separating monovalent ions from multivalent ions in water according to claim 1, wherein in S1, the electrodialysis membrane (3) comprises at least one pair of a cation membrane and a monovalent anion permselective membrane;
the cation membrane and the monovalent anion permselective membrane are disposed between the electrodes.
3. The method for separating monovalent ions from multivalent ions in water according to claim 2, wherein the cation membrane and the monovalent anion permselective membrane are sequentially assembled in pairs in an overlapping manner, so as to divide the water to be treated into a plurality of fresh water chambers (1) and a plurality of concentrated water chambers (2).
4. The method for separating monovalent ions and multivalent ions in water according to claim 3, wherein in S1, the water to be treated is separated into fresh water and first concentrated water by the electrodialysis membrane (3), wherein the fresh water is formed by:
monovalent anions move to the positively charged electrode, permeate the monovalent anion permselective membrane and reach the concentrated water chamber (2);
multivalent anions move to the positively charged electrode, cannot permeate the monovalent anion permselective membrane, and are trapped in the fresh water chamber (1);
the fresh water chambers (1) are communicated to form fresh water outlet, the content of monovalent anions in the fresh water outlet is lower than that of the water to be treated, and the content of polyvalent anions is not lower than that of the water to be treated.
5. The method for separating monovalent ions and multivalent ions in water according to claim 3, wherein in S1, the water to be treated is separated into fresh water and first concentrated water by the electrodialysis membrane (3), wherein the first concentrated water is formed by:
monovalent anions and polyvalent anions move to the positively charged electrode, are intercepted by the cation membrane in the moving direction, and are intercepted in the concentrated water chamber (2);
positive ions move to the negatively charged electrode, are intercepted by the monovalent negative ions in the moving direction selectively permeating an ion membrane and are intercepted in the concentrated water chamber (2);
and the concentrated water chambers (2) are communicated to form a first concentrated water outlet, and the content of monovalent anions and cations in the first concentrated water outlet is higher than that of the water to be treated.
6. The separation device for monovalent ions and multivalent ions is characterized by comprising a fresh water chamber (1) and a concentrated water chamber (2), wherein the fresh water chamber (1) and the concentrated water chamber (2) are separated by an electrodialysis membrane (3);
the electrodialysis membrane (3) comprises at least one pair of a cation membrane and a monovalent anion permselective membrane.
7. The separation device of monovalent ions and multivalent ions according to claim 6, wherein the cation membrane and the monovalent anion permselective membrane are sequentially assembled in pairs in an overlapping manner, so as to divide the separation device into a plurality of fresh water chambers (1) and a plurality of concentrated water chambers (2).
8. The separation device of monovalent ion and multivalent ion according to claim 7, further comprising a nanofiltration device (4), wherein the nanofiltration device is connected with the water inlet end of the nanofiltration device after a plurality of the fresh water chambers (1) are communicated.
9. The separation device of monovalent ions and multivalent ions according to claim 8, further comprising a reverse osmosis device (5), wherein the water outlet end of the reverse osmosis device is connected after the plurality of concentrated water chambers (2) are communicated;
the water inlet end of the reverse osmosis device is connected with the water outlet end of the nanofiltration device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110280669.0A CN113003806A (en) | 2021-03-16 | 2021-03-16 | Method and device for separating monovalent ions and multivalent ions in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110280669.0A CN113003806A (en) | 2021-03-16 | 2021-03-16 | Method and device for separating monovalent ions and multivalent ions in water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113003806A true CN113003806A (en) | 2021-06-22 |
Family
ID=76408182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110280669.0A Pending CN113003806A (en) | 2021-03-16 | 2021-03-16 | Method and device for separating monovalent ions and multivalent ions in water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113003806A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716083A (en) * | 2022-02-14 | 2022-07-08 | 唐山钢铁集团有限责任公司 | Industrial strong brine zero-discharge treatment system and method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007289953A (en) * | 2006-03-31 | 2007-11-08 | Osaka Kensetsu Kk | Method for producing salt water, salt, and bittern using sea water as raw material, and salt water, salt, and bittern |
| US20100116663A1 (en) * | 2008-11-12 | 2010-05-13 | Davis Thomas A | Recovery of regenerant electrolyte |
| WO2016161511A1 (en) * | 2015-04-07 | 2016-10-13 | Saltworks Technologies Inc. | Process and apparatus for multivalent ion desalination |
| WO2017181696A1 (en) * | 2016-04-21 | 2017-10-26 | 广州市心德实业有限公司 | Method for treating and recycling brine wastewater containing sodium chloride and sodium sulfate |
| CN108793522A (en) * | 2018-07-14 | 2018-11-13 | 浙江大维高新技术股份有限公司 | A kind of desulfurization wastewater concentration decrement process |
| CN109650608A (en) * | 2017-10-12 | 2019-04-19 | 华东理工大学 | It is a kind of using chemical method-nanofiltration-it is reverse osmosis-electrodialysis integrate concentrated seawater softening and concentration technology |
-
2021
- 2021-03-16 CN CN202110280669.0A patent/CN113003806A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007289953A (en) * | 2006-03-31 | 2007-11-08 | Osaka Kensetsu Kk | Method for producing salt water, salt, and bittern using sea water as raw material, and salt water, salt, and bittern |
| US20100116663A1 (en) * | 2008-11-12 | 2010-05-13 | Davis Thomas A | Recovery of regenerant electrolyte |
| WO2016161511A1 (en) * | 2015-04-07 | 2016-10-13 | Saltworks Technologies Inc. | Process and apparatus for multivalent ion desalination |
| WO2017181696A1 (en) * | 2016-04-21 | 2017-10-26 | 广州市心德实业有限公司 | Method for treating and recycling brine wastewater containing sodium chloride and sodium sulfate |
| CN109650608A (en) * | 2017-10-12 | 2019-04-19 | 华东理工大学 | It is a kind of using chemical method-nanofiltration-it is reverse osmosis-electrodialysis integrate concentrated seawater softening and concentration technology |
| CN108793522A (en) * | 2018-07-14 | 2018-11-13 | 浙江大维高新技术股份有限公司 | A kind of desulfurization wastewater concentration decrement process |
Non-Patent Citations (1)
| Title |
|---|
| 蔡可芬等: "《功能材料》", 31 May 1988, 冶金工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716083A (en) * | 2022-02-14 | 2022-07-08 | 唐山钢铁集团有限责任公司 | Industrial strong brine zero-discharge treatment system and method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104370405B (en) | A kind for the treatment of process of high rigidity height salinity wastewater zero discharge | |
| US9206060B1 (en) | Method for purifying liquids | |
| CN107055713B (en) | High-hardness salt-containing water concentration method based on monovalent cation selective electrodialysis | |
| Yao et al. | Zero discharge process for dyeing wastewater treatment | |
| CN105906111A (en) | Method for separating salt from coal-chemical-industry wastewater through electroosmosis technique | |
| CN106396232B (en) | Zero-discharge system and method for high-salt printing and dyeing wastewater | |
| CN105502790A (en) | Desulfurization wastewater treatment system | |
| CN104071808A (en) | Method for preparing industrial salt through separation, evaporation and crystallization of coal chemical strong brine | |
| CN107098530A (en) | A kind of positive osmosis treatment system of chloro alcali wastewater and handling process | |
| CN103739132A (en) | High-salinity industrial wastewater reusing treatment process | |
| CN107640860A (en) | A kind of saliferous industrial wastewater desalination reuse technology of calcic magnesium ion, sulfate ion | |
| CN105417801A (en) | Method and system for extracting fresh water from sewage with synergy of forward osmosis and electrodialysis | |
| CN113105025B (en) | Combined treatment method for regenerating high-concentrated-salt wastewater by sodium ion exchanger | |
| CN108793517A (en) | A kind for the treatment of process of high COD leather-making waste waters with high salt | |
| CN108218101B (en) | Low-cost treatment and recycling method for high-salt-content gas field water | |
| CN113562924A (en) | Treatment system and method for resource utilization of high-salinity wastewater in ferrous metallurgy | |
| CN102527237B (en) | Method for removing mono-valent negative ion inorganic salt by using nano-filtration constant solvent of forward osmosis technology | |
| CN102815833A (en) | Membrane-process treatment and reusing technique for oxalic production wastewater containing nitric acid | |
| KR20140145309A (en) | The manufacturing process development of Processed deep seawater using NF/RO/ED membrane connection system | |
| CN113003806A (en) | Method and device for separating monovalent ions and multivalent ions in water | |
| CN113023990B (en) | Method for treating high-salinity water in steel plant | |
| CN112607942A (en) | Seawater recycling treatment system and process | |
| CN209890428U (en) | Harmless treatment system for printing and dyeing high-concentration wastewater | |
| CN106673144B (en) | A kind of electric nanofiltration device with low salt rejection rate and high rejection to organics rate | |
| CN105439346A (en) | Auto-precipitation pretreatment method of high-salt wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210622 |
|
| RJ01 | Rejection of invention patent application after publication |