CN111762853A - Liquid anode and method for enriching and separating anions in water body by using same - Google Patents
Liquid anode and method for enriching and separating anions in water body by using same Download PDFInfo
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- CN111762853A CN111762853A CN202010567975.8A CN202010567975A CN111762853A CN 111762853 A CN111762853 A CN 111762853A CN 202010567975 A CN202010567975 A CN 202010567975A CN 111762853 A CN111762853 A CN 111762853A
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- 239000007788 liquid Substances 0.000 title claims abstract description 91
- 150000001450 anions Chemical class 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 29
- 238000000034 method Methods 0.000 title description 23
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 58
- 239000002351 wastewater Substances 0.000 claims abstract description 28
- 239000002608 ionic liquid Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000012528 membrane Substances 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 46
- 239000000178 monomer Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000007785 strong electrolyte Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
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- 239000011148 porous material Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
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- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910017251 AsO4 Inorganic materials 0.000 claims description 3
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- 150000002500 ions Chemical group 0.000 claims description 3
- BGDTWOQNFJNCKH-UHFFFAOYSA-N n-ethyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(CC)CC=C BGDTWOQNFJNCKH-UHFFFAOYSA-N 0.000 claims description 3
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- 238000000926 separation method Methods 0.000 claims description 3
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- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 2
- 125000002228 disulfide group Chemical group 0.000 claims description 2
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 claims description 2
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- 239000011737 fluorine Substances 0.000 claims description 2
- 229910021645 metal ion Chemical group 0.000 claims description 2
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- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 26
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- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
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- 238000005266 casting Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
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- 238000012546 transfer Methods 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 239000003463 adsorbent Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 230000007665 chronic toxicity Effects 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
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- IIRDTKBZINWQAW-UHFFFAOYSA-N hexaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCO IIRDTKBZINWQAW-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013048 microbiological method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000005838 radical anions Chemical class 0.000 description 1
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- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a liquid anode, which consists of hydrophobic liquid, a hydrophilic solid carrier film and a conductive electrode, wherein the hydrophobic liquid is filled in a bag made of the hydrophilic solid carrier film, and then the conductive electrode is placed in the bag to prepare the liquid anode; wherein the hydrophobic liquid is hydrophobic ionic liquid or hydrophobic conductive liquid; compared with the traditional anode material, the liquid anode has simple preparation method, large specific surface area of the electrode and large capacitance, organically couples physical adsorption, chemical adsorption and electric adsorption, is suitable for treating complex anions in water, and solves the problems of small current density, incapability of efficiently transferring mass, low electrolysis efficiency and large power consumption when the conventional electrode is used for electrolyzing low-concentration wastewater.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method for enriching and separating anions in a water body by using a liquid anode.
Background
The presence of ionic contaminants in the form of anions in water is very high, most of which have a certain potential or significant toxicity and can cause water environmental problems of varying degrees. Nitrate (NO) in water3 -) Phosphate (PO)4 3-) The most direct harm is to cause water eutrophication, deteriorate the sensory performance of the water, destroy the ecological balance of the water and the like. Perchlorate (ClO) existing in natural environment4 -) Although acute toxicity cannot be caused to organisms in water bodies, the influence of the chronic toxicity cannot be ignored. The heavy metals in the water exist mostly in the form of metal hydrate ions with positive charges, and the small heavy metals exist in the states of metal complex anions and oxygen acid radical anions. Dichromate (Cr)2O7 2-) Arsenate (AsO)4 3-) And the like are considered as anion pollutants with strong toxicity to the environment and human bodies, and have great harm to the health of human bodies.
The existing process for removing anionic pollutants in water comprises a chemical reduction method, a chemical precipitation method, an adsorption and ion exchange method, a membrane separation method, a microbiological method, an electrochemical method and the like. The adsorption method and the electrochemical method are widely applied, but the adsorption method has the problems of difficult preparation, poor reproducibility, high cost and the like of a novel adsorption material; the electrochemical method mainly utilizes the action of an external electric field to electrolyze the wastewater to promote anions to migrate to the anode and deposit on the surface of the anode, thereby realizing the removal of the anions in the wastewater. In addition, the electrode material has great influence on the electrolytic process, different anode materials can influence the anion removal effect, and in order to realize the removal of larger anions, most of the anode materials in the current electrolytic process are noble metal oxides, so the cost is too high.
Therefore, the invention considers the design of a new liquid anode material, the design and synthesis conditions of the anode material are mild, and the design and synthesis can be finished under the conditions of a common laboratory; the designability is strong, and the hydrophobic liquid can be modified, controlled or changed to meet different design requirements. The electrode is coupled with physical adsorption, chemical adsorption and electric adsorption in the using process to efficiently enrich and separate complex anion components in water, and has the advantages of simple operation, large adsorption capacity of adsorption materials, low operation working voltage, economy and high efficiency. Thereby efficiently treating the complex anionic components in the wastewater at low cost.
Disclosure of Invention
Aiming at the problem that anions in the wastewater are difficult to effectively remove, the invention provides the liquid anode which is simple to operate, large in adsorption capacity of an adsorption material, low in operation working voltage, economic and efficient; the electrode consists of hydrophobic liquid, a hydrophilic solid carrier film and a conductive electrode, wherein the hydrophobic liquid is used as an electrode main body, the hydrophilic film is used as the solid carrier film, and the conductive electrode is used as an electrifying medium; the hydrophobic liquid is filled in a bag made of a hydrophilic solid carrier film, and then the conductive electrode is placed in the bag to prepare the liquid anode.
The adsorption of the liquid anode to the anions is a mass transfer process, and the anions can permeate the membrane without obstruction due to the extremely strong hydrophilicity, high specific surface area and high porosity of the hydrophilic membrane and are finally adsorbed and removed by the core main body (hydrophobic liquid) of the electrode; the hydrophobic liquid can be ionic liquid or polymer liquid added with a conductive medium and a hydrophobic monomer, and the electrode is simple to prepare and wide in application range; after the conductive electrode arranged in the solid carrier film is electrified with an external power supply, the exchange current density of the whole liquid electrode is accelerated, the electrode activity is enhanced, and under the action of electromigration, anions in the wastewater continuously migrate to the electric field anode region, so that the removal rate of the liquid anode to the anions is enhanced.
The hydrophobic liquid is hydrophobic ionic liquid or hydrophobic conductive liquid.
The hydrophobic ionic liquid is one of functional ionic liquids in which specific functional groups such as quaternary ammonium groups, thiourea substituent groups, thioether substituent groups, sulfydryl, disulfide functional groups or metal ion substituent groups are grafted on cations; it may also be a hydrophobic dicationic ionic liquid, for example [ (O)5C10)-(BZbenim)2][PF6]2、[C3(C1Im)2][Tf2N]2、[Cn(Mim)2][NTf2]2(n =8-16), and the like.
The hydrophobic conductive liquid consists of 0.05-0.15mmol/L strong electrolyte aqueous solution, 0.3-1.0mmol/L hydrophobic monomer solution and 0.75-1.5mmol/L polymer solution according to the volume ratio of 1-5:1-4.3: 2-6.8; wherein the strong electrolyte solution can be one of sodium chloride solution, sodium sulfate solution, sodium carbonate solution, potassium hydroxide solution, ammonium sulfate solution, etc.; the hydrophobic monomer can be one of acrylate monomer, styrene, methacrylate, vinyl trimethylsilane, fluorine-containing acrylate, tert-butyl acrylamide, polybutyl acrylate and the like; the polymer solution is one of cationic polyacrylamide solution, 3-acrylamide propyl-trimethyl ammonium chloride solution, dimethyl diallyl ammonium chloride solution, mixed solution of diallyl ethylamine and dimethylformamide (volume ratio is 3-7: 0.5-1.0), cetyl trimethyl ammonium bromide solution and the like; the hydrophobic ionic liquid can be prepared by a conventional method.
The hydrophilic immobilized membrane is one of a hydrophilic PVC membrane, a PVA hydrophilic membrane, an ePTFE/PP hydrophilic membrane, a PVDF hydrophilic membrane, a nano super-hydrophilic membrane and the like, the contact angle of the hydrophilic immobilized membrane is 0-15 degrees, the pore diameter is 0.5-20 mu m, and the thickness is 0.12-0.2 mm.
The conductive electrode is a Cu electrode, a Pt electrode, a Fe electrode, a Zn electrode or a graphite electrode, the position of the conductive electrode can be flexibly adjusted, the conductive electrode can be arranged in the middle of the liquid anode or fixed on two sides, and the position of the conductive electrode does not influence the performance of the liquid electrode.
Another object of the present invention is to apply the above liquid anode to the enrichment and separation of anions in wastewater, wherein the anions in the wastewater to be treated are F-、Cl-、Br-、Cr2O7 2-、NO3 -、PO4 3-、AsO4 3--And SO4 2-One or more of the following; before use, the liquid anode is soaked in the wastewater to be treated at the temperature of 15-80 ℃ and the pH value of 3-122-24h, then externally connecting a power supply in the presence of a cathode, and applying 3-15V voltage to treat the wastewater.
When the ionic liquid is selected as the electrode adsorption main body, the advantages of large potential window, strong conductivity and good stability of the ionic liquid and the double adsorption performance of the ionic liquid to anions are fully utilized; when the hydrophobic conductive liquid is selected as the electrode adsorption core unit, the removal of anions in water can be greatly improved, under the action of electromigration, the anions in the wastewater continuously migrate to the electric field anode area, and the adsorption of a liquid anode to the anions is enhanced; compared with the traditional anode material, the liquid electrode has the advantages of simple preparation method, large specific surface area of the electrode and large capacitance, organically couples physical adsorption, chemical adsorption and electric adsorption, is suitable for treating complex anions in water, and solves the problems of small current density, incapability of realizing efficient mass transfer, low electrolysis efficiency and large power consumption when the conventional electrode is used for electrolyzing low-concentration wastewater.
The invention has the advantages that:
1. the liquid anode has the advantages of low raw material cost, easy preparation, good stability, convenient operation, large adsorption capacity for different anions in water compared with the traditional adsorbent, and good reliability;
2. the liquid anode has strong designability, the hydrophobic liquid can be selected from ionic liquid and self-made hydrophobic conductive liquid, and the synthesis process of the two liquids is simple and has great adjustability. Physical adsorption, chemical adsorption and electric adsorption are organically coupled, so that the target anion removal is enhanced;
3. the liquid anode has the advantages of large specific surface area, large capacitance, recyclable electrode, long service time, no loss of quality and flexible application. The method can be used for pretreatment of wastewater containing high-concentration target anions, and anions in the wastewater are removed to a certain extent through the treatment of the electrode, so that the method is beneficial to subsequent biochemical treatment of the wastewater and is also suitable for advanced treatment of the wastewater containing low-concentration anions in water.
Drawings
FIG. 1 is a schematic view of the structure of a liquid anode according to examples 1 and 4;
FIG. 2 is a schematic view of a liquid anode structure according to example 2;
fig. 3 is a schematic structural view of a liquid anode in example 3.
Detailed Description
The present invention is further described in detail by the following specific embodiments, but the scope of the present invention is not limited to the following embodiments.
Example 1: the liquid anode structure is shown in figure 1 and comprises a hydrophilic PVC (polyvinyl chloride) solid-supported membrane 1, hydrophobic dicationic ionic liquid 2 and an Fe electrode 3; filling hydrophobic liquid into a bag made of a hydrophilic solid-supported membrane, and then placing a conductive electrode into the bag to obtain a liquid anode;
the preparation method of the hydrophilic PVC immobilized membrane comprises the following steps: dissolving 3.6g of polyvinyl chloride in 38.6g of dimethylacetamide solution, stirring until the polyvinyl chloride is completely dissolved, adding 0.41g of vinyl acetate, continuously stirring, adding 1.5g of nano-alumina powder in the stirring process, immediately adding 0.3g of dispersing agent sodium hexametaphosphate, finally adding 2.0g of pore-forming agent polyvinylpyrrolidone, uniformly stirring for 24 hours, sealing, standing, defoaming, casting the casting membrane solution on a clean glass plate, scraping to form a membrane, volatilizing for 60 seconds, putting into 25% ethanol solidification solution, taking out the glass plate after the membrane is automatically stripped, soaking the membrane in the solidification solution for 24 hours, and washing with distilled water to obtain the hydrophilic membrane, wherein the prepared hydrophilic membrane is prepared according to the method in CN101513593B 'hydrophilic polyvinyl chloride membrane and preparation method', the prepared immobilized membrane has a contact angle of 10 degrees, a pore diameter of 15 mu m and a membrane thickness of 0.15 mm;
the hydrophobic liquid is hexaethyleneglycol bis (N-benzyl-benzene-imidazolyl) hexafluorophosphate [ (O)5C10)-(BZbenim)2][PF6]2Dicationic ionic liquids, their synthesis and performance studies, referred to as "Guo Yan-benzimidazolyl Dicationic liquids]The university of south china, 2017.
At room temperature, 50mL [ (O)5C10)-(BZbenim)2][PF6]2Placing in a bag made of hydrophilic PVC solid carrier film, and placing Fe electrode in the bag to obtain liquid anode(ii) a When in use, the liquid anode is firstly placed in Cl under the condition of not adding an external power supply-Adsorbing in wastewater with concentration of 500mg/L, pH of 10 for 24h, with wastewater water temperature of 30 ℃, placing liquid electrode in wastewater to be treated for 24h before electrifying, and treating with Cl-Removing rate up to 63%, placing into graphite cathode, applying 8V voltage to graphite cathode and liquid anode, reacting for 75min, and adding Cl-The removal rate reaches 94 percent.
Example 2: the liquid anode structure is shown in fig. 2 and comprises a hydrophilic PVA solid supported membrane 1, hydrophobic conductive liquid 2 and a Cu electrode 3; filling hydrophobic liquid into a bag made of a hydrophilic solid-supported membrane, and then placing a conductive electrode into the bag to obtain a liquid anode;
the preparation method of the hydrophilic PVA immobilized membrane comprises the following steps: weighing 6g of PVA, putting the PVA into 54mL of distilled water, heating to completely dissolve the PVA in the distilled water, adding 4.20g of glacial acetic acid into the solution, uniformly stirring to prepare a membrane preparation solution, standing and soaking for later use. Wetting clean polyester filter cloth with water, flatly paving the filter cloth on a glass plate, flatly paving the filter cloth without bubbles, pouring a film-making solution on the filter cloth, scraping the filter cloth into a liquid film with uniform thickness by using a glass rod, drying the prepared film in an oven at 60 ℃ for 3 hours, naturally air-drying the film at room temperature for more than 24 hours, and soaking the film in water to remove the film after the film is completely dried; the preparation refers to the method in' Guanfu Wei, preparation of filter cloth-PVA hydrophilic membrane and research on oil-water emulsion treatment [ J ]. Chinese scientific and technical information, 2009(16): 116-;
the hydrophobic conductive liquid consists of 0.1mmol/L strong electrolyte aqueous solution, 0.3mmol/L hydrophobic monomer solution and 1.5mmol/L polymer solution according to the volume ratio of 2:1: 2; the preparation method comprises the following steps:
weighing sodium chloride, dissolving the sodium chloride in 20mL of distilled water at room temperature, uniformly mixing to prepare 0.1mmol/L strong electrolyte aqueous solution, taking 20mL of 1.5 mmol/L3-acrylamidopropyl-trimethyl ammonium chloride solution, putting the solution into 20mL of sodium chloride electrolyte, stirring for 30min, and finally adding 10mL of hydrophobic monomer tert-butyl acrylamide after the two solutions are fully mixed; the preparation process of the hydrophobic monomer refers to' Liudong root, Wanghaibo, Limianhao, and the likeSynthesis of [ J]The method in Yunnan chemical industry, 2006, 33(5), "electromagnetic stirring for 2h to obtain hydrophobic conductive liquid; a built-in metal Cu electrode is arranged, and a liquid anode is arranged in F under the condition of not adding an external power supply-Adsorbing in waste water with concentration of 50mg/L, pH of 7 for 2h at the temperature of 25 ℃ to determine F in the system-The removal rate of the anode reaches 15 percent, then Fe is put into the anode as a cathode, and F is obtained after the Fe cathode and the liquid anode are externally connected with an 8V power supply and electrified for 135 minutes-The removal rate of the catalyst can reach 92.5 percent.
Example 3: the liquid anode structure is shown in fig. 3, and comprises a hydrophilic PVDF solid supported membrane 1, a hydrophobic conductive liquid 2 and a graphite electrode 3; filling hydrophobic liquid into a bag made of a hydrophilic solid-supported membrane, and then placing a conductive electrode into the bag to obtain a liquid anode;
the hydrophilic PVDF immobilized membrane was prepared as follows: PVDF is selected as a material, N, N-dimethylacetamide (DMAc) is selected as a solvent, polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG) are selected as additives, wherein the amounts of PVDF and PVP are respectively 18% and 14%, the molecular weight of PEG is 200, PVDF, PVP and PEG are mixed and dissolved in DMAc, standing, defoaming and filtering are carried out to form a membrane casting solution, heating is carried out until curing is carried out, vacuum defoaming is carried out in a vacuum box again, then a frame type coating device is used for forming a membrane on plate glass, the membrane is placed in a coagulating bath, and after the membrane is automatically removed, the membrane is soaked in alcohol and distilled water solution for about 4 hours to obtain the composite membrane; the preparation refers to the methods in Liu Qian, Zhu Xiao Lian, Zhang Shuxiang, the preparation of hydrophilic polyvinylidene fluoride membrane [ J ], Shandong chemical industry, 2015, 44(8):35-36. "; the contact angle is 8 degrees, the pore size is 18 mu m, and the film thickness is 0.14 mm;
hydrophobic conductive liquid the hydrophobic conductive liquid is composed of 0.15mmol/L strong electrolyte aqueous solution, 0.7mmol/L hydrophobic monomer solution and 1.2mmol/L polymer solution according to the volume ratio of 3:1:6, and is specifically prepared as follows:
weighing cationic polyacrylamide, dissolving the cationic polyacrylamide in 30mL of distilled water to prepare 1.2mmol/L of polymer solution, stirring until the cationic polyacrylamide is completely dissolved, adding 15mL of 0.15mmol/L of sodium sulfate solution, stirring uniformly, adding 5mL of tert-butyl acrylamide, and synthesizing a hydrophobic monomer by using the method disclosed in the specification of 'Liudong root, Wanghao, Limian Miao, and the like'; electromagnetically stirring for 1h to be viscous to obtain the hydrophobic conductive liquid;
with a graphite electrode inside, AsO in wastewater4 3-The concentration is 120mg/L, NO3 -The concentration is 150mg/L, PO4 3-The concentration is 100mg/L, the wastewater with the pH value of 2 and the temperature of 50 ℃ is not electrically adsorbed for 2.5h, and the AsO in the system is measured4 3-、NO3 -And PO4 3-The removal rate of (2) is 8%, 12% and 10%, then placing the graphite cathode, the graphite cathode and the liquid anode are externally connected with a 10V power supply, electrifying for 120min, and measuring to obtain AsO4 3-The removal rate of the catalyst reaches 87 percent, and NO is3 -And PO4 3-The removal rates of (a) and (b) were 90% and 96%, respectively.
Example 4: the liquid anode structure is shown in fig. 1 and comprises a super-hydrophilic nanofiber membrane 1, hydrophobic conductive liquid 2 and a Cu electrode 3;
the hydrophilic nanofiber immobilized membrane is prepared by mixing trifluoroacetic acid and dichloromethane in a ratio of 2:3 to prepare a mixed solvent, adding polyester chips into the mixed solvent, magnetically stirring at room temperature until the polyester chips are completely dissolved to obtain a polyester solution, wherein the ratio of the polyester chips to the mixed solvent is 3:6, adding cyclodextrin, citric acid and sodium hypophosphite into the polyester solution in a ratio of 1.5:0.5:2.3, magnetically stirring at room temperature until the polyester chips are completely dissolved to obtain a polyester mixed solution, performing electrostatic spinning on the polyester mixed solution to obtain a polyester nanofiber membrane, and performing heating treatment at 145 ℃ for 1.5 hours to obtain the superhydrophilic nanofiber membrane; the specific preparation process refers to: CN107747165A 'a super hydrophilic polyester nanofiber membrane and a method for preparing the same'; the contact angle is 0 degree, the pore size is 15 mu m, and the film thickness is 0.13 mm;
the hydrophobic conductive liquid consists of 0.05mmol/L strong electrolyte aqueous solution, 1.0mmol/L hydrophobic monomer solution and 1.5mmol/L polymer solution according to the volume ratio of 1:3:6, and is prepared specifically as follows:
taking 5mL of potassium hydroxide solution to prepare 0.05mmol/L strong electrolyte aqueous solution in distilled water, weighing polybutyl acrylate, dissolving in 15mL of ethanol to prepare 1.0mmol/L of hydrophobic monomer solution, mixing and stirring the hydrophobic monomer solution and the strong electrolyte aqueous solution for 30min, finally adding 30mL of polymer liquid, wherein the polymer liquid is a mixed solution (volume ratio is 6.5: 1.0) of diallyl ethylamine and dimethylformamide, and stirring with a glass rod for 10min to obtain hydrophobic conductive liquid;
built-in Cu electrode, Cr in waste water2O7 2-The concentration is 400mg/L, Br-The wastewater with the concentration of 250mg/L, the pH value of 10 and the temperature of 40 ℃ is not electrically adsorbed for 2.5h, and Cr in a system is measured2O7 2-And Br-The removal rate of the graphite electrode is 20 percent and 15 percent, then a graphite cathode, a graphite electrode and a liquid anode are externally connected with a 13V power supply, and after being electrified for 120min, Cr is obtained by measurement2O7 2-The removal rate of (B) is up to 96 percent, Br-The removal rate of (2) is up to 85%.
Claims (9)
1. A liquid anode, characterized by: the liquid anode consists of hydrophobic liquid, a hydrophilic solid carrier film and a conductive electrode, namely the hydrophobic liquid is filled in a bag made of the hydrophilic solid carrier film, and then the conductive electrode is placed in the bag to prepare the liquid anode.
2. A liquid anode as claimed in claim 1, wherein: the hydrophobic liquid is hydrophobic ionic liquid or hydrophobic conductive liquid.
3. A liquid anode as claimed in claim 2, wherein: the hydrophobic ionic liquid is one of functional ionic liquids with cation grafted with quaternary ammonium groups, thiourea substituent groups, thioether substituent groups, sulfydryl, disulfide functional groups or metal ion substituent groups, or is hydrophobic dicationic ionic liquid.
4. A liquid anode as claimed in claim 3, wherein: the hydrophobic dicationic ionic liquid is [ (O)5C10)-(BZbenim)2][PF6]2、[C3(C1Im)2][Tf2N]2、[Cn(Mim)2][NTf2]2(n = 8-16).
5. A liquid anode as claimed in claim 2, wherein: the hydrophobic conductive liquid consists of 0.05-0.15mmol/L strong electrolyte solution, 0.3-1.0mmol/L hydrophobic monomer solution and 0.75-1.5mmol/L polymer solution in the volume ratio of 1-5:1-4.3:2-6.8, wherein the strong electrolyte solution is one of sodium chloride solution, sodium sulfate solution, sodium carbonate solution, potassium hydroxide solution and ammonium sulfate solution; the hydrophobic monomer is one of acrylate monomer, styrene, methacrylate, vinyl trimethylsilane, fluorine-containing acrylate, tert-butyl acrylamide and polybutyl acrylate; the polymer solution is one of cationic polyacrylamide solution, 3-acrylamide propyl trimethyl ammonium chloride solution, dimethyl diallyl ammonium chloride solution, mixed solution of diallyl ethylamine and dimethyl formamide, cetyl trimethyl ammonium bromide solution and the like.
6. A liquid anode as claimed in claim 1, wherein: the hydrophilic immobilized membrane is one of a hydrophilic PVC membrane, a PVA hydrophilic membrane, an ePTFE/PP hydrophilic membrane, a PVDF hydrophilic membrane and a nano super-hydrophilic membrane, the contact angle of the hydrophilic immobilized membrane is 0-15 degrees, the pore diameter is 0.5-20 mu m, and the thickness is 0.12-0.2 mm.
7. A liquid anode as claimed in claim 1, wherein: the conductive electrode is a Cu electrode, a Pt electrode, a Fe electrode, a Zn electrode or a graphite electrode.
8. Use of a liquid anode according to any one of claims 1 to 7 for the enrichment of anions in separation waste water, characterized in that: the anion in the wastewater to be treated is F-、Cl-、Br-、Cr2O7 2-、NO3 -、PO4 3-、AsO4 3--And SO4 2-And the like.
9. The use of claim 8, wherein: before use, the liquid anode is placed in wastewater to be treated at the temperature of 15-80 ℃ and the pH value of 3-12, soaked for 2-24h, and then externally connected with a power supply in the presence of a cathode, and a voltage of 3-15V is applied to treat the wastewater.
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