CN108786479B - Cation exchange membrane, preparation thereof and application thereof in separation of alkane/olefin - Google Patents
Cation exchange membrane, preparation thereof and application thereof in separation of alkane/olefin Download PDFInfo
- Publication number
- CN108786479B CN108786479B CN201810533946.2A CN201810533946A CN108786479B CN 108786479 B CN108786479 B CN 108786479B CN 201810533946 A CN201810533946 A CN 201810533946A CN 108786479 B CN108786479 B CN 108786479B
- Authority
- CN
- China
- Prior art keywords
- cation exchange
- exchange membrane
- olefin
- separation
- membrane
- 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.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/422—Electrodialysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
Abstract
The invention belongs to the technical field of membrane separation, and particularly relates to a cation exchange membrane, preparation thereof and application thereof in alkane/alkene separation. The preparation method comprises the steps of mixing N, N-dimethylformamide as a phase transfer agent with choline lysine salt ionic liquid, polyacrylonitrile and cation exchange resin to prepare a cation exchange membrane loaded with the ionic liquid, wherein the cation exchange membrane can be used for separating olefin/alkane under the action of an electric field, and a complex with positive charge formed by olefin and silver ions permeates through the cation exchange membrane to realize the separation of the olefin and the alkane under the action of the electric field; silver ions in the complex are reduced on the cathode electrode and olefins are released. The cathode electrode for depositing silver simple substance can change the current direction to be the anode and change the silver into silver ion again for recycling. The preparation method is simple, the cost is low, and the prepared cation exchange membrane has stable performance and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a cation exchange membrane, preparation thereof and application thereof in alkane/alkene separation.
Background
Olefins are important basic feedstocks for the petrochemical industry. In the industry, the production of olefins by catalytic cracking of petroleum or by Fischer-Tropsch synthesis after gasification of coal, faces the problem of separation of olefins from paraffins. Because the size and boiling point of the same carbon olefin and alkane molecules are similar, the traditional low-temperature distillation separation method has high energy consumption, complex process and large investment, and in order to reduce the investment and the energy consumption, the chemical industry always tries to use a new separation method to replace a low-temperature distillation method, such as reactive distillation, molecular sieve separation, membrane separation and the like. The membrane separation is one of the most promising alternative methods for separating olefin/alkane, and has the characteristics of low energy consumption, low investment, environmental friendliness and the like.
The separation mechanism of the membrane is divided into two types of dissolution diffusion and promotion of transfer. The membrane based on the dissolution diffusion mechanism has low selectivity to olefin and alkane or low permeability, for example, when ethane and ethylene are separated, the separation factor is only 4-5, and the membrane has no practical application value. The FTM separation technology is to introduce transition metal ion as carrier into the membrane and to react reversibly with olefin to form intermediate compound for completing olefin transfer and separation. FTM technology is highly selective and is considered to be an efficient and valuable olefin/alkane separation process. Ag+Etc. a complex may be formed between the transition metal and the olefin, which complex may be decomplexed by increasing the temperature or reducing the pressure. Many researchers have prepared facilitated transfer membranes with silver salts immobilized in the membrane as a support for olefin/alkane separation. However, in the use of the above-mentioned membrane, silver salt is reduced to elemental silver, which results in a short membrane life and a reduced ability to separate olefin/alkane.
The ionic liquid has designability, the performance of promoting the diffusion membrane to separate the olefin/alkane is enhanced by adding a plurality of ionic liquids, and the ionic liquid has conductivity.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a cation exchange membrane, which utilizes N, N-dimethylformamide as a phase transfer agent to be mixed with choline lysine ionic liquid, polyacrylonitrile and cation exchange resin to prepare the cation exchange membrane loaded with the ionic liquid.
Another object of the present invention is to provide a cation exchange membrane prepared by the above preparation method, which can separate olefin/alkane under the action of an electric field.
It is a further object of the present invention to provide the use of the above cation exchange membranes.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a cation exchange membrane comprises the following steps;
(1) mixing cation exchange resin with polyacrylonitrile to obtain a base membrane;
(2) mixing choline lysine salt ionic liquid with N, N-dimethylformamide to obtain a mixed solution; then adding the mixed solution into the base film prepared in the step (1), stirring, and removing bubbles to obtain viscous liquid;
(3) pressing the viscous liquid prepared in the step (2) into a film, and cleaning the film to obtain a cation exchange membrane;
the cation exchange resin in the step (1) is preferably a strong-acid cation exchange resin;
the strong-acid cation exchange resin is preferably an exchange group of sulfonic acid group (-SO)3H) The cation exchange resin of (1);
the dosage of the cation exchange resin in the step (1) is preferably 10-70% of the mass of the basement membrane;
the cation exchange resin described in step (1) is preferably subjected to the following pretreatment:
drying, crushing and sieving the cation exchange resin;
the screening is preferably a screen of 150-300 meshes;
the dosage of the choline lysine salt ionic liquid in the step (2) is preferably 10-20% of the mass of the basement membrane;
the dosage of the N, N-dimethylformamide in the step (2) is preferably 2mL/g of basal membrane;
the bubbles in the step (2) are removed preferably by vacuum;
the film pressing in the step (2) is preferably to press a film on a glass plate by casting viscous liquid;
preferably, deionized water is adopted for cleaning for 2-4 times in the step (3);
a cation exchange membrane prepared by the preparation method;
the thickness of the cation exchange membrane is preferably 4-6 mm;
the ion exchange membrane is preferably stored in deionized water;
the application of the cation exchange membrane in the separation of alkane/olefin;
the application of the cation exchange membrane in separating alkane/olefin comprises the following steps:
fixing the cation exchange membrane in the middle of an electrolytic cell, and dividing the electrolytic cell into an anode chamber and a cathode chamber; inert electrodes are arranged at two sides of the groove and are connected with a direct current power supply; putting mixed solution of olefin/alkane and silver nitrate solution into the anode chamber, wherein silver ion-olefin complex is formed by olefin and silver ions in silver nitrate at the anode of the electrolytic cell, and nitric acid solution is put into the cathode cell; turning on direct current to perform electrodialysis;
the final concentration of the silver nitrate in the anode chamber is preferably 0.1-1 mol/L;
the final concentration of the silver nitrate in the anode chamber is further preferably 0.25 mol/L;
the concentration of the nitric acid is preferably 1 mol/L;
the current intensity of the electrodialysis is preferably 0.001-0.01A;
the current intensity of the electrodialysis is more preferably 0.002A;
the principle of the invention is as follows:
the invention uses N, N-dimethyl formamide as a phase transfer agent to mix with choline lysine ionic liquid, polyacrylonitrile and cation exchange resin to prepare a cation exchange membrane loaded with the ionic liquid, wherein the cation exchange membrane can be used for electrodialysis separation of alkane/olefin, the cation exchange membrane is used for dividing an electrolytic cell into an anode chamber and a cathode chamber, the anode chamber and the cathode chamber are respectively provided with an inert electrode and connected with a direct current power supply, the anode chamber is provided with mixed solution of alkene/alkane and silver nitrate solution, the cathode chamber is provided with nitric acid solution, and in the anode chamber, the alkene and silver ions in silver nitrate form a silver ion-alkene complex; then, the direct current is switched on, the silver ion-olefin complex passes through the cation exchange membrane under the action of the electric field and moves to the cathode chamber, and the alkane cannot be complexed with the silver ion and still stays in the anode chamber, so that the separation of the olefin and the alkane is realized; silver ions in the silver ion-olefin complex are reduced at the cathode electrode, and olefin is released. The cathode electrode for depositing silver can change the current direction to be the anode electrode, and the silver can be changed into silver ions again for recycling (figure 1).
Compared with the prior art, the invention has the following advantages and effects:
(1) n, N-dimethylformamide is used as a phase transfer agent and is mixed with choline lysine ionic liquid, polyacrylonitrile and cation exchange resin to prepare the cation exchange membrane loaded with the ionic liquid, and the ionic liquid is added to promote the diffusion of olefin.
(2) The cation exchange membrane loaded with the ionic liquid is used for electrodialysis separation of alkane/olefin, wherein a complex with positive charge formed by olefin and silver ions permeates the cation exchange membrane under the action of an electric field to realize separation of the olefin and the alkane; silver ions in the complex are reduced on the cathode electrode and olefins are released. The cathode electrode for depositing silver simple substance can change the current direction to be the anode and change the silver into silver ion again for recycling.
(3) The preparation method is simple, the cost is low, and the prepared cation exchange membrane has stable performance and is suitable for industrial production.
Drawings
FIG. 1 is a schematic diagram of the principle of separation of olefins from alkanes using a cation exchange membrane.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Sulfonic acid group (-SO) in examples3H) The cation exchange resin, choline lysine salt ionic liquid and other reagents are all purchased from the market;
example 1
(1) The exchange group is sulfonic group (-SO)3H) Drying and crushing the cation exchange resin, sieving the crushed cation exchange resin by a 150-mesh sieve, and mixing the crushed cation exchange resin and polyacrylonitrile in a 50ml beaker to obtain a base membrane with the total mass of 5g, wherein the dosage of the cation exchange resin is 10 percent of the mass of the base membrane;
(2) fusing choline lysine salt ionic liquid and N, N-dimethylformamide in a 50ml beaker to obtain a mixed solution; then adding the mixed solution into the base film prepared in the step (1), stirring, and extracting bubbles by using vacuum to obtain uniform viscous liquid; wherein the dosage of the choline lysine salt ionic liquid is 10 percent of the mass of the basement membrane, and the dosage of the N, N-dimethylformamide is 10 ml;
(3) and (3) casting the viscous liquid prepared in the step (2) on a glass plate to form a film, naturally dropping the formed film from the glass plate, washing for 3 times by using deionized water to obtain a cation exchange membrane, and storing the cation exchange membrane in the deionized water for later use.
The cation exchange membrane prepared by the implementation has the thickness of 6mm, the water content of 57.67 percent and the ion exchange capacity of 5.31mmol/g-1The film resistance was 6.9. omega./cm2。
Example 2
(1) Drying and crushing cation exchange resin, sieving the crushed cation exchange resin by a 300-mesh sieve, and mixing the crushed cation exchange resin and polyacrylonitrile in a 50ml beaker to obtain a base membrane with the total mass of 5g, wherein the dosage of the cation exchange resin is 50% of the mass of the base membrane;
(2) fusing choline lysine salt ionic liquid and N, N-dimethylformamide in a 50ml beaker to obtain a mixed solution; then adding the mixed solution into the base film prepared in the step (1), stirring, and extracting bubbles by using vacuum to obtain uniform viscous liquid; wherein the dosage of the choline lysine salt ionic liquid is 20 percent of the mass of the basement membrane, and the dosage of the N, N-dimethylformamide is 10 ml;
(3) and (3) casting the viscous liquid prepared in the step (2) on a glass plate to form a film, naturally dropping the formed film from the glass plate, washing for 3 times by using deionized water to obtain a cation exchange membrane, and storing the cation exchange membrane in the deionized water for later use.
The thickness of the cation exchange membrane prepared by the implementation is 4mm, the water content is 64.24 percent, and the ion exchange capacity is 6.43mmol/g-1The film resistance was 9.38. omega./cm2。
Example 3
(1) Drying and crushing cation exchange resin, sieving the crushed cation exchange resin by a 240-mesh sieve, and mixing the crushed cation exchange resin and polyacrylonitrile in a 50ml beaker to obtain a base membrane with the total mass of 5g, wherein the dosage of the cation exchange resin is 70% of the mass of the base membrane;
(2) fusing choline lysine salt ionic liquid and N, N-dimethylformamide in a 50ml beaker to obtain a mixed solution; then adding the mixed solution into the base film prepared in the step (1), stirring, and extracting bubbles by using vacuum to obtain uniform viscous liquid; wherein the dosage of the choline lysine salt ionic liquid is 15 percent of the mass of the basement membrane, and the dosage of the N, N-dimethylformamide is 10 ml;
(3) and (3) casting the viscous liquid prepared in the step (2) on a glass plate to form a film, naturally dropping the formed film from the glass plate, and then washing the film for 4 times by using deionized water to obtain a cation exchange membrane, wherein the cation exchange membrane is stored in the deionized water for later use.
The cation exchange membrane prepared by the implementation has the thickness of 5mm, the water content of 51.07 percent and the ion exchange capacity of 4.19mmol/g-1The film resistance was 7.5. omega./cm2。
Effects of the embodiment
The cation exchange membrane (commercial CMI-7000 type cation exchange membrane as a control) prepared in examples 1 to 3 was fixed in the middle of an electrolytic cell (with a notch of 100mm × 200mm) to divide the electrolytic cell into an anode chamber and a cathode chamber; inert electrodes (10 mm x 20mm platinum mesh electrodes are adopted as cathode and anode electrodes) are placed at two sides of the groove and are connected with a direct current power supply. 10ml of mixed solution with the mass ratio of 1-hexene to n-hexane being 1:1 and 30ml of silver nitrate solution with the silver ion concentration being 1mol/L are placed into the anode chamber, and 30ml of nitric acid solution with the concentration being 1mol/L is placed into the cathode chamber. Turning on direct current with current intensity of 0.002A, and performing electrolysis (FIG. 1);
the experiment result shows that in a 4-hour experiment, the separation selectivity of the cation exchange membrane prepared in example 1 on olefin is as high as 6.6, which is 4.95 times that of the current commercial CMI-7000 type cation exchange membrane, the concentration of the olefin is increased to 85%, and the concentration is 1.7 times.
In a 4-hour experiment, the separation selectivity of the cation exchange membrane prepared in example 2 on olefin is 3.7, which is 2.8 times that of the current commercial CMI-7000 type cation exchange membrane, the concentration of olefin is improved to 79 percent, and the concentration is 1.6 times.
In a 4-hour experiment, the separation selectivity of the cation exchange membrane prepared in example 3 on olefin is up to 9.5, which is 7.1 times that of the current commercial CMI-7000 type cation exchange membrane, the concentration of the olefin is increased to 91%, and the concentration is 1.8 times.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a cation exchange membrane is characterized by comprising the following steps;
(1) mixing cation exchange resin with polyacrylonitrile to obtain a base membrane;
(2) mixing choline lysine salt ionic liquid with N, N-dimethylformamide to obtain a mixed solution; then adding the mixed solution into the base film prepared in the step (1), stirring, and removing bubbles to obtain viscous liquid;
(3) and (3) pressing the viscous liquid prepared in the step (2) into a film, and cleaning the film to obtain the cation exchange membrane.
2. The method for preparing a cation exchange membrane according to claim 1, characterized in that:
the cation exchange resin in the step (1) is strong-acid cation exchange resin;
the dosage of the cation exchange resin in the step (1) is 10-70% of the mass of the base membrane.
3. The method for preparing a cation exchange membrane according to claim 1, characterized in that:
the dosage of the choline lysine salt ionic liquid in the step (2) is 10-20% of the mass of the basement membrane.
4. The method for preparing a cation exchange membrane according to claim 1, characterized in that:
the dosage of the N, N-dimethylformamide in the step (2) is 2mL/g of basal membrane.
5. The method for preparing a cation exchange membrane according to claim 1, characterized in that:
and (4) cleaning for 2-4 times by using deionized water.
6. A cation exchange membrane characterized by being prepared by the preparation method of any one of claims 1 to 5.
7. The cation exchange membrane of claim 6, wherein:
the thickness of the cation exchange membrane is 4-6 mm.
8. Use of the cation exchange membrane of claim 6 or 7 for the separation of alkanes/alkenes.
9. Use of a cation exchange membrane according to claim 8 for the separation of alkanes/alkenes, characterized in that it comprises the following steps:
fixing the cation exchange membrane in the middle of an electrolytic cell, and dividing the electrolytic cell into an anode chamber and a cathode chamber; inert electrodes are arranged at two sides of the groove and are connected with a direct current power supply; putting mixed solution of olefin/alkane and silver nitrate solution into the anode chamber, wherein silver ion-olefin complex is formed by olefin and silver ions in silver nitrate at the anode of the electrolytic cell, and nitric acid solution is put into the cathode cell; turning on direct current to perform electrodialysis.
10. Use of a cation exchange membrane according to claim 9 for the separation of alkanes/alkenes, characterized in that:
the current intensity of the electrodialysis is 0.001-0.01A.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810533946.2A CN108786479B (en) | 2018-05-29 | 2018-05-29 | Cation exchange membrane, preparation thereof and application thereof in separation of alkane/olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810533946.2A CN108786479B (en) | 2018-05-29 | 2018-05-29 | Cation exchange membrane, preparation thereof and application thereof in separation of alkane/olefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108786479A CN108786479A (en) | 2018-11-13 |
| CN108786479B true CN108786479B (en) | 2020-04-28 |
Family
ID=64089241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810533946.2A Active CN108786479B (en) | 2018-05-29 | 2018-05-29 | Cation exchange membrane, preparation thereof and application thereof in separation of alkane/olefin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108786479B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111318166B (en) * | 2018-12-14 | 2021-09-14 | Tcl科技集团股份有限公司 | Quantum dot purification method |
| CN112596270A (en) * | 2020-12-02 | 2021-04-02 | 明月镜片股份有限公司 | Novel infrared-proof lens |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1552875A1 (en) * | 2004-01-08 | 2005-07-13 | Korea Institute of Science and Technology | Facilitated transport membranes for an alkene hydrocarbon separation |
| CN101613481A (en) * | 2009-07-13 | 2009-12-30 | 清华大学 | A kind of method for preparing interpenetrating network type conducting film of poly ion liquid |
| CN102574060A (en) * | 2009-09-25 | 2012-07-11 | 陶氏环球技术有限责任公司 | Olefin selective membrane comprising an ionic liquid and a complexing agent |
| CN107875867A (en) * | 2017-11-09 | 2018-04-06 | 石河子大学 | A kind of faciliated diffusion film based on amino acid ion liquid and its preparation method and application |
-
2018
- 2018-05-29 CN CN201810533946.2A patent/CN108786479B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1552875A1 (en) * | 2004-01-08 | 2005-07-13 | Korea Institute of Science and Technology | Facilitated transport membranes for an alkene hydrocarbon separation |
| CN101613481A (en) * | 2009-07-13 | 2009-12-30 | 清华大学 | A kind of method for preparing interpenetrating network type conducting film of poly ion liquid |
| CN102574060A (en) * | 2009-09-25 | 2012-07-11 | 陶氏环球技术有限责任公司 | Olefin selective membrane comprising an ionic liquid and a complexing agent |
| CN107875867A (en) * | 2017-11-09 | 2018-04-06 | 石河子大学 | A kind of faciliated diffusion film based on amino acid ion liquid and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| Preparation and characterization of ABS/HIPS heterogeneous cation exchange membranes with various blend ratios of polymer binder;S.M. Hosseini, S.S. Madaeni, A.R. Khodabakhshi;《Journal of Membrane Science》;20100128;第351卷;第179页第2栏第15行-180页第1栏第27行，表2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108786479A (en) | 2018-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Merino-Garcia et al. | Electrochemical membrane reactors for the utilisation of carbon dioxide | |
| Liang et al. | Optimized desalination performance of high voltage flow-electrode capacitive deionization by adding carbon black in flow-electrode | |
| Wang et al. | The intensification technologies to water electrolysis for hydrogen production–A review | |
| Nie et al. | Electrophoretic deposition of carbon nanotubes–polyacrylic acid composite film electrode for capacitive deionization | |
| JP5897512B2 (en) | Method for electrolytic concentration of heavy water | |
| US8303781B2 (en) | Electrolytic cells and methods for the production of ammonia and hydrogen | |
| Palakkal et al. | Low-resistant ion-exchange membranes for energy efficient membrane capacitive deionization | |
| Wang et al. | Continuous desalination with a metal-free redox-mediator | |
| CN108786479B (en) | Cation exchange membrane, preparation thereof and application thereof in separation of alkane/olefin | |
| JP4907745B2 (en) | How to reduce carbon dioxide | |
| Li et al. | Ion-exchange polymers modified bacterial cellulose electrodes for the selective removal of nitrite ions from tail water of dyeing wastewater | |
| Gaikwad et al. | Polymer coated capacitive deionization electrode for desalination: a mini review | |
| CN112301373A (en) | Method for selective reduction of alkyne impurities in olefin by electrocatalysis | |
| Fang et al. | The impact of concentration in electrolyte on ammonia removal in flow-electrode capacitive deionization system | |
| CN110117807A (en) | A kind of two-dimensional material-transition metal hetero-junctions preparation of sections method | |
| Zhang et al. | Continuous electrochemical deionization by utilizing the catalytic redox effect of environmentally friendly riboflavin-5'-phosphate sodium | |
| KR20210069590A (en) | Water treatment apparatus and water treatment method using same | |
| Duan et al. | Potential of zero charge regulating highly selective removal of nitrate anions through capacitive deionization | |
| Lee et al. | Asymmetric cell design for decoupled hydrogen and oxygen evolution paired with V (II)/V (III) redox mediator | |
| CN107546038B (en) | A kind of concentration difference capacitor | |
| KR101526246B1 (en) | Composite Electrode For Water Treatment And Method For Manufacturing The Same And Water Treatment System | |
| CN102358637B (en) | Electrochemically enhancing multifunctional material adsorbing and fluorine removing system, and method thereof | |
| Chen et al. | Characteristics and vanadium adsorption performance of resin/carbon composite electrodes in capacitive deionization | |
| Ashrafizadeh et al. | A brief review on the recent achievements in flow-electrode capacitive deionization | |
| Kovtun et al. | ANALYSIS OF EXISTING METHODS FOR IMPROVING THE PHYSICAL AND CHEMICAL CONDITIONS OF THE ION EXCHANGE PROCESS IN WATER TREATMENT |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |