CN113830865A - Method for degrading venlafaxine in water and electrochemical treatment device - Google Patents
Method for degrading venlafaxine in water and electrochemical treatment device Download PDFInfo
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- 229960004688 venlafaxine Drugs 0.000 title claims abstract description 121
- PNVNVHUZROJLTJ-UHFFFAOYSA-N venlafaxine Chemical compound C1=CC(OC)=CC=C1C(CN(C)C)C1(O)CCCCC1 PNVNVHUZROJLTJ-UHFFFAOYSA-N 0.000 title claims abstract description 121
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000000593 degrading effect Effects 0.000 title claims abstract description 40
- 238000006731 degradation reaction Methods 0.000 claims abstract description 44
- 230000015556 catabolic process Effects 0.000 claims abstract description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 35
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- 229910002804 graphite Inorganic materials 0.000 claims description 21
- 239000010439 graphite Substances 0.000 claims description 21
- 239000012528 membrane Substances 0.000 claims description 20
- 238000007747 plating Methods 0.000 claims description 18
- 238000005868 electrolysis reaction Methods 0.000 claims description 15
- 238000005341 cation exchange Methods 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000005342 ion exchange Methods 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 229910003460 diamond Inorganic materials 0.000 claims description 7
- 239000010432 diamond Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- HJPBEXZMTWFZHY-UHFFFAOYSA-N [Ti].[Ru].[Ir] Chemical compound [Ti].[Ru].[Ir] HJPBEXZMTWFZHY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- ZACYQVZHFIYKMW-UHFFFAOYSA-N iridium titanium Chemical compound [Ti].[Ir] ZACYQVZHFIYKMW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical compound [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 abstract description 20
- 230000001590 oxidative effect Effects 0.000 abstract description 19
- 230000003647 oxidation Effects 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 7
- 239000013543 active substance Substances 0.000 abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 16
- 230000008569 process Effects 0.000 description 10
- TVWHTOUAJSGEKT-UHFFFAOYSA-N chlorine trioxide Chemical compound [O]Cl(=O)=O TVWHTOUAJSGEKT-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000005684 electric field Effects 0.000 description 5
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 238000006056 electrooxidation reaction Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000935 antidepressant agent Substances 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical class NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000003010 cation ion exchange membrane Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
- C02F1/4695—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis electrodeionisation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
- C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46147—Diamond coating
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- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
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- 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
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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Abstract
The application belongs to the technical field of water treatment, and particularly relates to a method for degrading venlafaxine in water and an electrochemical treatment device for degrading venlafaxine in water. The method for degrading venlafaxine in water comprises the following steps: constructing an electrolytic device comprising: the ion exchange membrane is used for separating the anode tank from the cathode tank, the anode tank is internally provided with anode and anolyte, and the cathode tank is internally provided with cathode and catholyte; the anolyte contains sulfate ions and chloride ions; venlafaxine was added to the anode cell for electrochemical degradation. According to the method for degrading venlafaxine in water, by means of the chlorine synergistic oxidation technology, active species with stronger oxidizability are generated in the system under the condition of inputting the same electric quantity, and the types of active substances in the system are enriched, so that venlafaxine in water is efficiently and quickly degraded in an oxidizing mode, and the cost is saved.
Description
Technical Field
The application belongs to the technical field of water treatment, and particularly relates to a method for degrading venlafaxine in water and an electrochemical treatment device for degrading venlafaxine in water.
Background
Venlafaxine is a phenethylamine derivative, a bicyclic atypical antidepressant drug, and is now widely used worldwide due to its excellent properties. Venlafaxine cannot be completely metabolized after being ingested by a human body and is often discharged in a parent form, but the venlafaxine cannot be effectively degraded by the conventional sewage treatment process, so that the venlafaxine is often discharged into a natural water body along with effluent of a sewage treatment plant. Venlafaxine has been detected in various natural environments such as lakes, rivers, soil and the like. Venlafaxine is difficult to naturally degrade, can be enriched in organisms, and has non-negligible toxicity to the organisms, so that the development of corresponding technology is urgently needed to realize effective degradation of venlafaxine.
Disclosure of Invention
The application aims to provide a method for degrading venlafaxine in water and an electrochemical treatment device for degrading venlafaxine in water, and aims to solve the problem that the existing venlafaxine is difficult to naturally degrade to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for degrading venlafaxine in water, comprising the steps of:
constructing an electrolysis apparatus comprising: the device comprises an anode tank, a cathode tank and an ion exchange diaphragm, wherein the anode tank and the cathode tank are separated by the ion exchange diaphragm, an anode and an anolyte are arranged in the anode tank, and a cathode and a catholyte are arranged in the cathode tank; the anolyte contains sulfate ions and chloride ions;
venlafaxine was added to the anode cell for electrochemical degradation.
Further, in the anolyte, the concentration of sulfate ions is 0.01-1 mol/L.
Further, in the anolyte, the concentration of chloride ions is 1-100 mmol/L.
Further, the catholyte contains sulfate ions with the concentration of 0.05-1 mol/L.
Further, the anolyte comprises at least one of sodium sulfate, magnesium sulfate and potassium sulfate.
Further, the anolyte comprises at least one of sodium chloride, magnesium chloride and potassium chloride.
Further, the conditions of electrochemical degradation include: the current density at the anode and the cathode is 0.1-200 mA/cm2Degrading for 0.5-200 min under the condition of (1).
Further, the anode is selected from DSA electrodes (dimensionally stable anodes).
Further, the cathode is selected from a metal electrode or a carbon electrode.
Further, the anode is selected from: at least one of a titanium ruthenium plating electrode, a titanium iridium plating electrode, a titanium ruthenium iridium plating electrode and a boron-doped diamond film electrode.
Further, the cathode is selected from: at least one of platinum electrode, stainless steel electrode, titanium electrode, graphite electrode, carbon black electrode, and carbon nanotube electrode.
Further, the ion exchange membrane is selected from cation exchange membranes.
Further, after the electrochemical degradation is carried out for 30min, the concentration of the venlafaxine in the anolyte is not higher than 2.5 mg/L.
In a second aspect, the present application provides an electrochemical treatment device for degrading venlafaxine in water, comprising: anode tank, cathode cell and ion exchange diaphragm, anode tank and cathode cell are separated with the ion exchange diaphragm, be provided with positive pole and anolyte in the anode tank, set up negative pole and catholyte in the cathode cell, the positive pole with the negative pole is connected with the power respectively, and sets up a pair ofly at least, including sulfate radical ion and chloride ion in the anolyte.
Further, the anode is selected from DSA electrodes.
Further, the cathode is selected from a metal electrode or a carbon electrode.
Further, the ion exchange membrane is selected from cation exchange membranes.
Further, the anode is selected from: at least one of a titanium ruthenium plating electrode, a titanium iridium plating electrode, a titanium ruthenium iridium plating electrode and a boron-doped diamond film electrode.
Further, the cathode is selected from: at least one of platinum electrode, stainless steel electrode, titanium electrode, graphite electrode, carbon black electrode, and carbon nanotube electrode.
In the first aspect of the present application, in the method for degrading venlafaxine in water, during the electrolysis process, sulfate ions lose electrons on the surface of the anode to generate SO4 ·－And a small amount of S2O8 2－Water is ionized to OH, and chloride ions are oxidized to Cl and ClO3 －The oxidizing substances have strong oxidizing capability and can attack a plurality of sites in venlafaxine molecules, wherein Cl & is easy to react with electron-rich groups to attack benzene rings in venlafaxine, so that the venlafaxine is rapidly degraded. On the other hand, the anolyte contains sulfate ions and chloride ions, so that the conductivity of the anolyte can be effectively improved, the degradation rate of the venlafaxine in water is further improved, the degradation time of the venlafaxine is shortened, and the energy utilization rate is improved. According to the method for degrading the venlafaxine in the water, by means of the chlorine synergistic oxidation technology, under the condition of inputting the same electric quantity, active species with stronger oxidizability are generated in the system, and the types of the active substances in the system are enriched, so that the venlafaxine in the water is more efficiently and quickly degraded by oxidation, the efficiency is improved, the cost is saved, the treatment method is simple to operate, the condition is mild, and the feasibility is high.
The electrochemical treatment device for degrading venlafaxine in water provided by the second aspect of the application is realized by electrochemical treatmentAfter the chemical treatment device is electrified, an electric field is formed between the anode and the cathode, and then the electrolyte in the anode tank and the electrolyte in the cathode tank are initiated to generate electrochemical reaction, so that the venlafaxine in the electrolyte can be effectively degraded. In addition, the electrolyte with anode tank contains sulfate ion and chloride ion, and during electrochemical reaction, the anode can oxidize the sulfate ion, chloride ion, water, etc. in the electrolyte to produce SO with strong oxidizing property4·－、S2O8 2－OH, Cl and ClO3 －And the active substances and the free radicals are equal, so that the venlafaxine is degraded in the anode tank, and the degradation efficiency of the venlafaxine is obviously improved. The application provides a degradation aquatic venlafaxine electrochemical treatment device, through chlorine oxidation technology in coordination, under the condition of the equal electric quantity of input, produced the stronger active species of oxidizing nature in the system, richened the active material kind in the system simultaneously to high-efficient fast oxidation degradation aquatic venlafaxine, raise the efficiency.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is an electrochemical treatment device for degrading venlafaxine in water, provided by an embodiment of the present application;
wherein, in the figures, the respective reference numerals: 1-anode 2-anode tank 3-ion exchange diaphragm 4-cathode 5-cathode tank
FIG. 2 is a graph showing the relationship between the electrolysis time and the venlafaxine removal rate in examples 1 to 4 of the present application and comparative example 1.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The first aspect of the embodiments of the present application provides a method for degrading venlafaxine in water, comprising the following steps:
s10, constructing an electrolysis device, wherein the electrolysis device comprises: the device comprises an anode tank 2, a cathode tank 5 and an ion exchange diaphragm 3, wherein the anode tank 2 and the cathode tank 5 are separated by the ion exchange diaphragm 3, an anode 1 and an anolyte are arranged in the anode tank 2, and a cathode 4 and a catholyte are arranged in the cathode tank 5; the anolyte contains sulfate ions and chloride ions;
s20, adding venlafaxine into the anode tank 2 for electrochemical degradation.
According to the method for degrading venlafaxine in water provided by the first aspect of the embodiment of the application, after the electrolytic device is constructed, venlafaxine is added into anolyte containing sulfate ions and chloride ions, and the power supply is switched on to carry out electrochemical degradation, on one hand, in the electrolytic process, the sulfate ions lose electrons on the surface of the anode 1 to generate SO4 ·－And a small amount of S2O8 2－Water is ionized to OH, and chloride ions are oxidized to Cl and ClO3 －The oxidizing substances have strong oxidizing capability and can attack a plurality of sites in venlafaxine molecules, wherein Cl & is easy to react with electron-rich groups to attack benzene rings in venlafaxine, so that the venlafaxine is rapidly degraded. On the other hand, the anolyte contains sulfate ions and chloride ions, which can effectively improve the conductivity of the electrolyte, thereby further improving the degradation rate of the venlafaxine in water and shortening the venlafaxineThe degradation time of the octane is prolonged, and the energy utilization rate is improved. In addition, the anode tank 2 and the cathode tank 5 in the constructed electrolytic device are separated by the ion exchange membrane 3, so that the active substances generated by anodic oxidation are effectively prevented from being reduced at the cathode and losing activity, and the degradation effect of venlafaxine is ensured. According to the method for degrading the venlafaxine in the water, by means of the chlorine synergistic oxidation technology, under the condition of inputting the same electric quantity, active species with stronger oxidizability are generated in the system, and the types of active substances in the system are enriched, so that the venlafaxine in the water is more efficiently and quickly degraded in an oxidizing mode, the efficiency is improved, the cost is saved, the treatment method is simple to operate, the conditions are mild, and the feasibility is high.
In some embodiments, in the step S10, the electrolytic device is configured to include: the anode comprises an anode 1, an anode tank 2, a cathode 4, a cathode tank 5, an ion exchange membrane 3 arranged between the anode tank 2 and the cathode tank 5, an anolyte contained in the anode tank 2 and a catholyte contained in the cathode tank 5, wherein the anolyte contains sulfate ions and chloride ions. After the anode 1 and the cathode 4 are electrified simultaneously, an electric field is formed between the anode 1 and the cathode 4, and then chemical reactions in the anode and cathode electrolytic cells are initiated, so that the venlafaxine in the anolyte can be electrochemically degraded.
In some embodiments, the anode 1 is selected from DSA electrodes (dimensionally stable anodes). The DSA anode adopted in the embodiment of the application mainly comprises base metal and a surface active coating plated with metal oxide with electrocatalytic activity, and has the advantages of high chemical stability, long service life and the like. In the electrochemical oxidation process, free radicals with strong oxidizing property can be generated on the surface of the DSA anode, SO that sulfate ions, chloride ions, water and the like in the anolyte are oxidized to generate SO with strong oxidizing property4 ·－、S2O8 2－OH, Cl and ClO3 －And the degradation rate of venlafaxine is obviously improved by the aid of free radicals and ions.
In some embodiments, anode 1 is selected from: at least one of a titanium ruthenium plating electrode, a titanium iridium plating electrode, a titanium ruthenium iridium plating electrode and a boron-doped diamond film electrode; these anodes 1 all generate radicals having a strong oxidizing property during the electrochemical oxidation.
In some embodiments, the cathode 4 is selected from a metal electrode or a carbon electrode, and the cathode 4 has high electrical conductivity, which can increase the electrochemical degradation rate. In some embodiments, the cathode 4 is selected from: at least one of platinum electrode, stainless steel electrode, titanium electrode, graphite electrode, carbon black electrode, and carbon nanotube electrode.
In some embodiments, the electrolysis apparatus has at least one pair of the anode 1 and the cathode 4, and a plurality of pairs of the anode 1 and the cathode 4 may be provided at the same time. In some embodiments, the electrodes may be rod-like or sheet-like in shape.
In some embodiments, the ion exchange membrane 3 is selected from cation exchange membranes, the ion exchange membrane 3 of the present example is used to separate the anode cell 2 from the cathode cell 5, and the cation exchange membrane used is a cation selective membrane, typically of the sulfonic acid type, with anchor groups and dissociable ions, such as sodium sulfonate where the anchor groups are sulfonate and the dissociable ions are sodium ions. The cation exchange membrane can be regarded as a polymer electrolyte, and is negatively charged, so that although original dissociated positive ions are dissociated into water by water molecules, the positive ions with positive charges can pass through the positive membrane through the action of an electric field when the membrane is electrified, and the negative ions cannot pass through the positive membrane because of the isotropic repulsion, so that the cation exchange membrane has selective permeability and effectively separates the anode tank 2 from the cathode tank 5. In some embodiments, cation ion exchange membrane 3 may be a nafion-117 ion exchange membrane 3.
In some embodiments, the material of the electrolytic cell in the electrolytic device is organic glass, so that the stability is good.
In some embodiments, the concentration of sulfate ions in the anolyte is 0.01-1 mol/L. In the anolyte of the embodiment of the application, sulfate ions not only have high conductivity, but also easily lose electrons in the electrochemical degradation process to generate SO4 ·－And a small amount of S2O8 2－The strong oxidizing substance can accelerateThe rate of oxidative degradation of venlafaxine. Sulfate ions with the concentration of 0.01-1 mol/L in the anolyte effectively ensure the degradation effect of strong oxidizing substances generated by electrolysis on venlafaxine. If the concentration of the sulfate ions is too low, the conductivity of the electrolyte is low; if the concentration of the sulfate ions is too high, incomplete dissolution of the sulfate radicals can be caused, and when the concentration of the sulfate ions is too high, the system mainly generates persulfate radicals through reaction, and the oxidation capacity of the persulfate radicals is weaker than that of the sulfate radicals, so that the degradation rate of the venlafaxine is not favorably improved. In some embodiments, the concentration of sulfate ions in the anolyte may be 0.01 to 0.1mol/L, 0.1 to 0.2mol/L, 0.2 to 0.5mol/L, 0.5 to 0.8mol/L, 0.8 to 1mol/L, and the like.
In some embodiments, the anolyte includes at least one of sodium sulfate, magnesium sulfate, and potassium sulfate. The sulfate ion concentration in the anolyte of the embodiment of the present application can be adjusted by sulfates such as sodium sulfate, magnesium sulfate, and potassium sulfate.
In some embodiments, the concentration of chloride ions in the anolyte is 1 to 100 mmol/L. In the anolyte of the embodiment of the application, the added chloride ions not only increase the concentration of anions in the anolyte and improve the conductivity of the anolyte, but also can generate Cl and ClO in the electrolysis process3 －An isostrong oxidizing substance, wherein, ClO3 －The oxidability is strong, and the venlafaxine can attack multiple sites of venlafaxine molecules; cl & easily reacts with the electron-rich groups to attack benzene rings in the venlafaxine, so that the rapid degradation of the venlafaxine can be realized, the degradation rate of the venlafaxine is greatly improved, and the energy utilization rate is improved. The concentration of chloride ions is 1-100 mmol/L, the venlafaxine has the best degradation efficiency, if the concentration of the chloride ions is too high, side reactions are increased, the generation of chlorine free radicals is not facilitated, and the degradation efficiency of the venlafaxine is reduced; if the concentration of the chloride ions is too low, active substances generated by electrolysis are reduced, the oxidizing capability is weak, and the venlafaxine is not easily oxidized and degraded. In some embodiments, the concentration of chloride ions in the anolyte may be 1-10 mmol/L, 10-20 mmol/L, 20-50 mmol/L, 50-80 mmol/L, 80-100 mmol/L, etc。
In some embodiments, the anolyte includes at least one of sodium chloride, magnesium chloride, and potassium chloride. In the anolyte of the embodiment of the present application, the chloride ion concentration can be adjusted by adding chlorides such as sodium chloride, magnesium chloride, and potassium chloride.
In some embodiments, the catholyte comprises sulfate ions at a concentration of 0.05 to 1 mol/L. The catholyte of the embodiment of the application contains conductive ions such as sulfate radicals and the like to form a conductive path with the anode, and the ion concentration ensures the conductive effect in the cathode slot 5.
In some embodiments, in step S20, venlafaxine is added to the anode tank 2, and the anode 1 and the cathode 4 are simultaneously energized, so that the venlafaxine in the anolyte can be electrochemically degraded.
In some embodiments, venlafaxine is added to the anode tank 2 at a current density of 0.1 to 200mA/cm at the anode 1 and cathode 42Under the condition (1), performing electrochemical degradation for 0.5-200 min. In the present example, partial reactions occurring in the electrochemical degradation process by energization of the electrolyzer are shown in the following formulas (1) to (7). Wherein, SO4 2－、Cl·、ClO3 －The substances have strong oxidizing property and can accelerate the degradation rate of the venlafaxine. The current density of the electrode is 0.1-200 mA/cm2The oxidation electrolysis efficiency of the electrode on sulfate ions, water and chloride ions is effectively ensured, and if the current density is too low, the electrolysis effects of the sulfate ions, the chloride ions, the water and the like in the electrolyte are not good; if the current density is too high, side reactions of ion oxidation electrolysis increase, and the efficiency of degradation of venlafaxine also decreases. The degradation time of 0.5-200 min ensures that the venlafaxine in the electrolyte is fully degraded, and if the degradation time is too short, the degradation is insufficient; if the degradation time is too long, unnecessary energy waste will be caused.
SO4 ·－+Cl－→SO4 2－+Cl· (1)
H2O→·OH+H· (2)
·OH+Cl－→OH－+Cl· (3)
2Cl－→Cl2(aq)+2e－ (4)
Cl2(aq)+H2O→HClO+Cl－+H+ (5)
ClO－+H2O→ClO3 －+4H++4e－ (7)
In some embodiments, the concentration of venlafaxine in the anolyte is no greater than 2.5mg/L after undergoing electrochemical degradation for 30 min. The method provided by the embodiment of the application can effectively degrade the venlafaxine in the water, so that the content of the venlafaxine in the degraded water is extremely low, the discharge standard is met, the effluent cannot pollute the natural environment, the biological enrichment risk of the venlafaxine is reduced, the toxicity to organisms is small, and the method is environment-friendly.
As shown in fig. 1, a second aspect of the embodiments of the present application provides an electrochemical treatment device for degrading venlafaxine in water, the electrochemical treatment device comprising: anode tank 2, cathode slot 5 and ion exchange diaphragm 3, anode tank 2 and cathode slot 5 are separated with ion exchange diaphragm 3, are provided with positive pole 1 and anolyte in anode tank 2, set up negative pole 4 and catholyte in cathode slot 5, and positive pole 1 and negative pole 3 are connected with the power respectively, and set up a pair ofly at least, include sulfate radical ion and chloride ion in the anolyte.
The electrochemical treatment device for degrading venlafaxine in water provided by the second aspect of the embodiment of the application comprises an anode 1, an anode tank 2, a cathode 4, a cathode tank 5, an ion exchange membrane 3 and electrolyte, wherein after the electrochemical treatment device is electrified, an electric field is formed between the anode 1 and the cathode 4, and then the anode tank and the cathode tank are triggeredThe electrolyte in the polar tank is subjected to electrochemical reaction, so that the venlafaxine in the electrolyte is effectively degraded. In addition, the anolyte comprises sulfate ions and chloride ions, and free radicals with strong oxidizing property can be generated on the surface of the anode in the electrochemical reaction process, SO that the sulfate ions, the chloride ions, water and the like in the anolyte are oxidized to generate SO with strong oxidizing property4 ·－、S2O8 2－、·OH、Cl·And ClO3 －And the free radicals and ions are equal, so that the venlafaxine is degraded in the anode tank, and the degradation efficiency of the venlafaxine is obviously improved. The embodiment of the application provides a degradation aquatic venlafaxine electrochemical treatment device, through chlorine oxidation technology in coordination, under the condition of the equal electric quantity of input, produced the stronger active species of oxidation in the system, enriched the active material kind in the system simultaneously to more high-efficient quick oxidative degradation aquatic venlafaxine, raise the efficiency.
In some embodiments, the anode 1 is selected from DSA electrodes. The DSA anode adopted in the embodiment of the application mainly comprises base metal and a surface active coating plated with metal oxide with electrocatalytic activity, and has the advantages of high chemical stability, long service life and the like. In the electrochemical oxidation process, free radicals with strong oxidizing property can be generated on the surface of the DSA anode, SO that sulfate ions, chloride ions, water and the like in the anolyte are oxidized to generate SO with strong oxidizing property4 ·－、S2O8 2－、·OH、Cl·And ClO3 －And the degradation rate of venlafaxine is obviously improved by the aid of free radicals and ions.
In some embodiments, anode 1 is selected from: at least one of a titanium ruthenium plating electrode, a titanium iridium plating electrode, a titanium ruthenium iridium plating electrode and a boron-doped diamond film electrode; these DSA anodes all generate radicals with strong oxidizing properties during electrochemical oxidation.
In some embodiments, the cathode 4 is selected from a metal electrode or a carbon electrode; these cathodes 4 have a high electrical conductivity and can increase the electrochemical degradation rate. In some embodiments, the cathode 4 is selected from: at least one of platinum electrode, stainless steel electrode, titanium electrode, graphite electrode, carbon black electrode, and carbon nanotube electrode.
In some embodiments, the electrolysis apparatus has at least one pair of the anode 1 and the cathode 4, and a plurality of pairs of the anode 1 and the cathode 4 may be provided at the same time.
In some embodiments, the electrodes may be rod-like or sheet-like in shape.
In some embodiments, the ion exchange membrane 3 is selected from cation exchange membranes, which in the present example are used to separate the anode cell 2 from the cathode cell 5, and the cation exchange membrane used is a cation selective membrane, typically of the sulfonic acid type, with anchor groups and dissociable ions, such as sodium sulfonic acid type where the anchor groups are sulfonate groups and the dissociable ions are sodium ions. The cation exchange membrane can be regarded as a polymer electrolyte, and is negatively charged, so that although original dissociated positive ions are dissociated into water by water molecules, the positive ions with positive charges can pass through the positive membrane through the action of an electric field when the membrane is electrified, and the negative ions cannot pass through the positive membrane because of the isotropic repulsion, so that the cation exchange membrane has selective permeability and effectively separates the anode tank 2 from the cathode tank 5.
In some embodiments, the material of the electrolytic cell in the electrolytic device is organic glass, so that the stability is good.
In order to make the details and operation of the above-mentioned embodiments of the present application clearly understandable to those skilled in the art and to make the progress of the method for degrading venlafaxine in water obvious, the above-mentioned technical solutions are illustrated by a plurality of examples.
In the following embodiments of the present application, the water to be treated is the same water sample, the pH of the water sample is 6.5, the water sample is 250mL, and 25mg/L venlafaxine is dissolved in the water sample. The concentration of sulfate was adjusted by adding different amounts of sodium sulfate and the concentration of chloride was adjusted by adding different amounts of sodium chloride. The power supply required in the experimental process is a direct current power supply.
Example 1
A method of degrading venlafaxine in water, comprising the steps of:
the method comprises the following steps of firstly, injecting a water sample to be treated into an anode tank, injecting electrolyte with sulfate radical concentration of 0.05M into a cathode tank, vertically and parallelly inserting a boron-doped diamond thin film electrode (BDD electrode) and a graphite cathode into the anode tank and the cathode tank respectively to immerse the BDD electrode and the graphite cathode in water, and correspondingly connecting the electrodes with a direct current power supply. The distance between the two electrodes is 1 cm.
The BDD electrode is 5cm multiplied by 10 cm; the size of the cathode graphite electrode is 5cm multiplied by 10 cm; under the electrification of a direct current power supply, the current at the two ends of the cathode and the anode is 100mA/cm2。
And thirdly, the treatment time is about 6.5min, the venlafaxine can reach 90% of removal rate, and the venlafaxine removal rate can reach 100% when the treatment time is 15 min.
Example 2
A method of degrading venlafaxine in water, comprising the steps of:
the method comprises the following steps of firstly, injecting a water sample to be treated into an anode tank, injecting electrolyte with sulfate radical concentration of 0.05M into a cathode tank, vertically and parallelly inserting a BDD electrode and a graphite cathode into the anode tank and the cathode tank respectively to immerse the BDD electrode and the graphite cathode into water, and correspondingly connecting the electrode with a direct-current power supply, wherein the sulfate radical concentration of the water sample to be treated is 0.1M, and the chloride ion concentration of the water sample to be treated is 10 mM. The distance between the two electrodes is 1 cm.
The BDD electrode is 5cm multiplied by 10 cm; the size of the cathode graphite electrode is 5cm multiplied by 10 cm; under the electrification of a direct current power supply, the current at the two ends of the cathode and the anode is 100mA/cm2。
And thirdly, the treatment time is about 4min, the venlafaxine can reach 90% of removal rate, and the venlafaxine removal rate can reach 100% when the treatment time is 10 min.
Example 3
A method of degrading venlafaxine in water, comprising the steps of:
the method comprises the following steps of firstly, injecting a water sample to be treated into an anode tank, injecting electrolyte with sulfate radical concentration of 0.05M into a cathode tank, vertically and parallelly inserting a BDD electrode and a graphite cathode into the anode tank and the cathode tank respectively to immerse the BDD electrode and the graphite cathode into water, and correspondingly connecting the electrode with a direct-current power supply, wherein the sulfate radical concentration of the water sample to be treated is 0.1M, and the chloride ion concentration of the water sample to be treated is 15 mM. The distance between the two electrodes is 1 cm.
The BDD electrode is 5cm multiplied by 10 cm; the size of the cathode graphite electrode is 5cm multiplied by 10 cm; under the electrification of a direct current power supply, the current at the two ends of the cathode and the anode is 100mA/cm2。
And thirdly, the treatment time is about 3min, the venlafaxine can reach 90% of removal rate, and the venlafaxine removal rate can reach 100% when the treatment time is 8 min.
Example 4
A method of degrading venlafaxine in water, comprising the steps of:
the method comprises the following steps of firstly, injecting a water sample to be treated into an anode tank, injecting electrolyte with sulfate radical concentration of 0.05M into a cathode tank, vertically and parallelly inserting a BDD electrode and a graphite cathode into the anode tank and the cathode tank respectively to immerse the BDD electrode and the graphite cathode into water, and correspondingly connecting the electrode with a direct-current power supply, wherein the sulfate radical concentration of the water sample to be treated is 0.1M, and the chloride ion concentration of the water sample to be treated is 20 mM. The distance between the two electrodes is 1 cm.
The BDD electrode is 5cm multiplied by 10 cm; the size of the cathode graphite electrode is 5cm multiplied by 10 cm; under the electrification of a direct current power supply, the current at the two ends of the cathode and the anode is 100mA/cm2。
And thirdly, the treatment time is about 2.5min, the venlafaxine can reach 90% of removal rate, and the venlafaxine removal rate can reach 100% when the treatment time is 5 min.
Comparative example 1
A method of degrading venlafaxine in water, comprising the steps of:
firstly, the sulfate radical concentration of a water sample to be treated is 0.1M, the water sample to be treated is injected into an anode tank, electrolyte with the sulfate radical concentration of 0.05M is injected into a cathode tank, a BDD electrode and a graphite cathode are respectively vertically and parallelly inserted into the anode tank and the cathode tank, the BDD electrode and the graphite cathode are immersed in water, and the electrodes are correspondingly communicated with a direct-current power supply. The distance between the two electrodes is 1 cm.
The BDD electrode is 5cm multiplied by 10 cm; the size of the cathode graphite electrode is 5cm multiplied by 10 cm; under the electrification of a direct current power supply, the current at the two ends of the cathode and the anode is 100mA/cm2。
And thirdly, the treatment time is about 8min, the venlafaxine can reach the removal rate of 90 percent, the venlafaxine removal rate reaches 100 percent, and the treatment time is more than 20 min.
The relationship between the electrolysis time and the venlafaxine removal rate in examples 1 to 4 and comparative example 1 is shown in FIG. 2, wherein no Cl is present-Representative of comparative example 1, 5mM Cl-Representative of example 1, 10mM Cl-Representative example 2, 15mM Cl-Representative example 3, 20mM Cl-Representing example 4, the ordinate represents the degradation rate of venlafaxine. As can be seen from the attached FIG. 2, the degradation rate of venlafaxine is significantly faster in examples 1 to 4 of the present application than in comparative example 1.
Compared with the comparative example 1 only adding sulfate ions, the method for degrading venlafaxine in water in the embodiments 1 to 4 of the application generates active species with stronger oxidizability in the system under the condition of inputting the same electric quantity through the chlorine synergistic oxidation technology, enriches the types of active substances in the system, can obviously shorten the degradation time of venlafaxine in water, efficiently and quickly remove venlafaxine in water, and can further adjust the degradation rate of venlafaxine by adding chloride ions and sulfate ions with different concentrations under the condition of inputting the same electric quantity, so that venlafaxine in water can be more efficiently and quickly oxidatively degraded, the efficiency is improved, the cost is saved, and the treatment method is simple to operate, mild in conditions and high in feasibility. The method for degrading venlafaxine in water provided by the embodiment of the application can effectively degrade the antidepressant drug venlafaxine, and meanwhile provides technical support for degrading the drug.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A method for degrading venlafaxine in water is characterized by comprising the following steps:
constructing an electrolysis apparatus comprising: the ion exchange membrane is used for separating the anode tank from the cathode tank, the anode tank is internally provided with anode and anolyte, and the cathode tank is internally provided with cathode and catholyte; the anolyte contains sulfate ions and chloride ions;
venlafaxine is added to the anolyte for electrochemical degradation.
2. The method for degrading venlafaxine in water according to claim 1, wherein the concentration of sulfate ions in the anolyte is 0.01 to 1 mol/L;
and/or the concentration of the chloride ions in the anolyte is 1-100 mmol/L;
and/or the catholyte contains sulfate ions with the concentration of 0.05-1 mol/L.
3. The method of degrading venlafaxine in water of claim 2, wherein the anolyte comprises at least one of sodium sulfate, magnesium sulfate, potassium sulfate;
and/or the anolyte comprises at least one of sodium chloride, magnesium chloride and potassium chloride.
4. A method of degrading venlafaxine in water according to any one of claims 1 to 3, wherein the conditions for electrochemical degradation comprise: the current density at the anode and the cathode is 0.1-200 mA/cm2Degrading for 0.5-200 min under the condition of (1).
5. The method of degrading venlafaxine in water of claim 4, wherein the anode is selected from the group consisting of DSA electrodes;
and/or the cathode is selected from a metal electrode or a carbon electrode.
6. The method of degrading venlafaxine in water of claim 4, wherein the anode is selected from the group consisting of: at least one of a titanium ruthenium plating electrode, a titanium iridium plating electrode, a titanium ruthenium iridium plating electrode and a boron-doped diamond film electrode;
and/or, the cathode is selected from: at least one of a platinum electrode, a stainless steel electrode, a titanium electrode, a graphite electrode, a carbon black electrode and a carbon nanotube electrode;
and/or, the ion exchange membrane is selected from a cation exchange membrane.
7. The method of degrading venlafaxine in water of claim 6, wherein the concentration of venlafaxine in the anolyte is no greater than 2.5mg/L after the electrochemical degradation is performed for 30 min.
8. An electrochemical treatment device for degrading venlafaxine in water, the electrochemical treatment device comprising: anode tank, cathode cell and ion exchange diaphragm, anode tank and cathode cell are used the ion exchange diaphragm separates, be provided with positive pole and anolyte in the anode tank, set up negative pole and catholyte in the cathode cell, the positive pole with the negative pole is connected with the power respectively, and sets up a pair ofly at least, including sulfate radical ion and chloride ion in the anolyte.
9. The electrochemical treatment apparatus for degrading venlafaxine in water according to claim 8, wherein the anode is selected from the group consisting of DSA electrodes;
and/or the cathode is selected from a metal electrode or a carbon electrode;
and/or, the ion exchange membrane is selected from a cation exchange membrane.
10. The electrochemical treatment apparatus for degrading venlafaxine in water according to claim 8, wherein the anode is selected from the group consisting of: at least one of a titanium ruthenium plating electrode, a titanium iridium plating electrode, a titanium ruthenium iridium plating electrode and a boron-doped diamond film electrode;
and/or, the cathode is selected from: at least one of platinum electrode, stainless steel electrode, titanium electrode, graphite electrode, carbon black electrode, and carbon nanotube electrode.
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