CN110759437B - Method for electrochemical-UV composite treatment of refractory organic matters - Google Patents
Method for electrochemical-UV composite treatment of refractory organic matters Download PDFInfo
- Publication number
- CN110759437B CN110759437B CN201910967504.3A CN201910967504A CN110759437B CN 110759437 B CN110759437 B CN 110759437B CN 201910967504 A CN201910967504 A CN 201910967504A CN 110759437 B CN110759437 B CN 110759437B
- Authority
- CN
- China
- Prior art keywords
- chlorine
- electrode
- electrochemical
- anode electrode
- lamp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 12
- 239000000460 chlorine Substances 0.000 claims abstract description 73
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 63
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 230000015556 catabolic process Effects 0.000 claims abstract description 32
- 238000006731 degradation reaction Methods 0.000 claims abstract description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- -1 chlorine ions Chemical class 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 230000005684 electric field Effects 0.000 claims abstract description 5
- 238000003487 electrochemical reaction Methods 0.000 claims abstract description 3
- IUBSYMUCCVWXPE-UHFFFAOYSA-N metoprolol Chemical compound COCCC1=CC=C(OCC(O)CNC(C)C)C=C1 IUBSYMUCCVWXPE-UHFFFAOYSA-N 0.000 claims description 9
- 229960002237 metoprolol Drugs 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 150000003841 chloride salts Chemical class 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 8
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 239000003317 industrial substance Substances 0.000 description 5
- 229940079593 drug Drugs 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000447 pesticide residue Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- CVOFKRWYWCSDMA-UHFFFAOYSA-N 2-chloro-n-(2,6-diethylphenyl)-n-(methoxymethyl)acetamide;2,6-dinitro-n,n-dipropyl-4-(trifluoromethyl)aniline Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl.CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O CVOFKRWYWCSDMA-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- HJPBEXZMTWFZHY-UHFFFAOYSA-N [Ti].[Ru].[Ir] Chemical compound [Ti].[Ru].[Ir] HJPBEXZMTWFZHY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229940035676 analgesics Drugs 0.000 description 1
- 239000000730 antalgic agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001754 anti-pyretic effect Effects 0.000 description 1
- 239000002221 antipyretic Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940124307 fluoroquinolone Drugs 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000003120 macrolide antibiotic agent Substances 0.000 description 1
- 229940041033 macrolides Drugs 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical compound [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 229940040944 tetracyclines Drugs 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 150000003952 β-lactams Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/32—Details relating to UV-irradiation devices
- C02F2201/322—Lamp arrangement
- C02F2201/3225—Lamps immersed in an open channel, containing the liquid to be treated
Landscapes
- Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention discloses a method for electrochemical-UV composite treatment of refractory organic matters, which comprises the step of placing an electrode group comprising at least one pair of anode electrode and cathode electrode connected with a power supply into a degradation pool, wherein the anode electrode is a chlorine evolution electrode. A UV lamp was placed close to the anode electrode. Injecting organic polluted water containing PPCPs into a degradation pool, and adjusting the concentration of chloride ions to be not less than 30 mg/L. The power supply is connected, so that an electric field is formed between the anode electrode and the cathode electrode, the chlorine-containing water is subjected to electrochemical reaction, and chlorine ions in the chlorine-containing water lose electrons on the surface of the anode electrode to generate free chlorine; the irradiation of the UV lamp enables free chlorine to further generate strong oxidizing substances comprising hydroxyl radicals and active chlorine, and the organic pollutants which are difficult to degrade in the chlorine-containing water are oxidized and degraded. The method is cooperated with electrochemical oxidation and UV, realizes high-efficiency removal of refractory organic pollutants by using chlorine contained in water, and has the advantages of simple method, good removal effect and the like.
Description
Technical Field
The invention relates to a method for electrochemical-UV composite treatment of refractory organic matters, belonging to the technical field of water treatment.
Background
The refractory organic matter includes polycyclic aromatic hydrocarbon, halohydrocarbon, heterocyclic compound, organic cyanide, organic phosphorus pesticide, surfactant, organic dye, etc. The treatment research is always a hotspot and a difficulty of the water pollution prevention and treatment research.
With the rapid development of economy and the improvement of living standard of people, medicines and personal care products (PPCPs for short) have attracted increasingly wide attention as a new class of organic pollutants. PPCPs are a wide variety of organic contaminants and are also increasing. The PPCPs compounds which can be detected at present comprise up to 101 compounds, including sulfonamides (19), fluoroquinolones (14), beta-lactams (11), macrolides (7), tetracyclines (7), bactericides (6), antipyretic and analgesic drugs (5) and other various antibiotic drugs (32). These organic pollutants present a potential threat to ecosystem and human health, and are mostly recalcitrant to removal using traditional or single water treatment processes, such as biological processes or single ozone, chlorine, and Ultraviolet (UV) light processes. Therefore, it is necessary to provide a high-efficiency treatment technology for refractory organic pollutants.
Comparison of UV/H2O2UV/chlorine is an emerging advanced oxidation technology, and has shown good removal effect in the aspect of removing the refractory organic pollutants. With UV/H2O2Compared with UV/chlorine, and HClO is more economical than H2O2The quantum absorption for UV is higher. The main reaction mechanism of the UV/chlorine process is shown in equations (1) to (6). Not only can non-selective HO be generated in the UV/chlorine process*Can also produce selectivityCl*、Cl2 *—And ClO*。HO*Is a strong oxidant, oxidation-reduction potential E02.8V, it is easily treated by natural organic substances, HCO, in actual water treatment3 -/CO3 -And (4) equal-matrix capture. Except for HO*，Cl*、Cl2 *—And ClO*The oxidant is also a high-efficiency oxidant, and the oxidation-reduction potentials of the oxidant are 2.4V, 2.0V and 1.5-1.8V respectively. There are many reports in the literature that the UV/chlorine process can achieve efficient removal of micro-contaminants in the class of pharmaceuticals and personal care products. Thus, UV/chlorine is an effective technique for the removal of pollutants in practical bodies of water.
HO*+HOCl→ClO*+H2O (3)
HO*+OCl—→ClO*+OH— (4)
Cl*+HOCl→ClO*+H++Cl— (5)
Cl*+OCl—→ClO*+Cl— (6)
Although UV/chlorine is considered a new and viable advanced oxidation technology, its application is somewhat limited. As in decentralized water treatment systems, NaClO and HClO are corrosive and HClO is extremely unstable, storage and transport of chlorine limits the application and spread of UV/chlorine for contaminant removal.
Disclosure of Invention
The invention aims to provide a method for electrochemical-UV composite treatment of refractory organic matters, which makes full use of the characteristic that chloride ions usually exist in water, generates an electric field through an electrode, and carries out chlorine evolution on a chlorine evolution anodeThe electrode surface generates the chloride ions in the chlorine-containing water into HClO and ClO-And Cl2And further reacting the free chlorine under the action of UV light to produce HO*And active chlorine (including Cl)*、Cl2 *—And ClO*) Thereby efficiently removing the organic pollutants in the water body.
The invention is realized by the following technical scheme:
the electrochemical-UV composite treatment method of refractory organic matter includes,
placing an electrode group comprising at least one pair of anode electrode and cathode electrode into a degradation pool, wherein the anode electrode and the cathode electrode are respectively connected with a power supply; the anode electrode is a chlorine evolution electrode;
disposing a UV lamp between and proximate to the anode electrode and the cathode electrode;
injecting organic polluted water containing refractory organics into a degradation pool, and adjusting the concentration of chloride ions in the organic polluted water to be not less than 30 mg/L;
connecting a power supply to form an electric field between the anode electrode and the cathode electrode, so that the chlorine-containing water is subjected to electrochemical reaction, and chlorine ions in the chlorine-containing water lose electrons on the surface of the anode electrode to generate HClO and ClO-And Cl2Free chlorine of (a); the UV light emitted by the UV lamp irradiates to enable free chlorine to further generate strong oxidizing substances including hydroxyl radicals and active chlorine, and the refractory organic pollutants in the chlorine-containing water are oxidized and degraded. The active chlorine includes Cl*、Cl2 *—And ClO*。
In the technical scheme, the organic polluted water is adjusted in chloride ion concentration by adding chloride salt, wherein the chloride salt is any one or a mixture of sodium chloride, magnesium chloride and potassium chloride.
In the technical scheme, the refractory organic matters comprise PPCPs, pesticide residues or industrial chemicals; the industrial chemicals include organic solvents, dyes or phenols.
In the above technical scheme, the anode electrode and the cathode electrode are both rod-shaped or sheet-shaped electrodes.
In the above technical scheme, the current density I of the anode electrode and the cathode electrode is 0<I≤500mA/cm2。
In the technical scheme, the UV lamp is arranged in the degradation pool and is immersed in the organic polluted water.
Among the above-mentioned technical scheme, the UV lamp is close to the degradation pond wall and sets up outside the degradation pond, and is provided with a degradation pond side wall of UV lamp and chooses for use the material that can see through the UV light.
In the technical scheme, the UV lamp is arranged above the degradation pool along the liquid level of the degradation pool.
In the technical scheme, the retention time of the chlorine-containing water in the degradation tank is 0.5-180 min.
The invention has the following advantages and beneficial effects: under the action of the cooperation of electrochemical oxidation and UV, pollutants which are difficult to degrade can be efficiently and quickly removed; the treatment method is simple and easy to implement, a large amount of free chlorine reagents such as chlorine, hypochlorous acid and hypochlorite are not required to be stored and consumed, and the cost is saved.
Drawings
FIG. 1 is a schematic view of an electrochemical-UV device according to one embodiment of the present invention.
Fig. 2 is a schematic view of an electrochemical-UV device according to another embodiment of the present invention.
Fig. 3 is a graph showing the removal effect of metoprolol drug by different processes. Wherein: □ denotes Electrolysis only (Electrolysis); ● denotes UV only irradiation (UV); tangle-solidup indicates electrochemical-UV/Chlorine (E-UV/Chlorine).
In the figure: 1-a power supply; 2-a cathode electrode; 3-an anode electrode; 4-UV lamp; and 5, a degradation tank.
Detailed Description
The following describes the embodiments and operation of the present invention with reference to the accompanying drawings.
The terms of orientation such as up, down, left, and right in the present specification are established based on the positional relationship shown in the drawings. The corresponding positional relationship may also vary depending on the drawings, and therefore, should not be construed as limiting the scope of protection.
As shown in fig. 1, an electrode group including at least one pair of an anode electrode 3 and a cathode electrode 2 is placed in a degradation tank 5, and the anode electrode 3 and the cathode electrode 2 are respectively connected to a power source 1. According to the requirement, the electrode group can be provided with a plurality of pairs of anode electrodes and cathode electrodes, and each pair of anode electrodes and cathode electrodes are connected with a power supply in a one-to-one correspondence mode. The lower part of the degradation tank 5 is provided with a water inlet, and the upper part is provided with a water outlet, so that water to be treated can enter and exit the degradation tank.
The anode electrode 3 is a chlorine-separating electrode, and comprises a titanium ruthenium-plated electrode, a titanium iridium-plated electrode and a titanium ruthenium iridium-plated electrode. The cathode electrode 2 is a metal electrode, including platinum, stainless steel or titanium electrode, or a carbon electrode, including graphite, carbon black, carbon nanotube electrode, etc. The anode electrode 3 and the cathode electrode 2 can be rod-shaped or sheet-shaped electrodes.
The UV lamp 4 is disposed near the anode electrode 3, and various types of mercury lamps or UV-LED lamps can be used as the UV lamp. In one embodiment, as shown in fig. 1, a UV lamp 4 is vertically inserted into the degradation tank 5 and disposed near the anode electrode 3. Another kind of embodiment is, the vertical 5 wall settings in degradation pond that are close to of UV lamp 4 are outside degradation pond 5, and are provided with 5 lateral wall of degradation pond of UV lamp 4 and select for use the material that can see through the UV light. In another embodiment, as shown in fig. 2, the UV lamp 4 is disposed above the degradation tank 5 against the liquid surface of the degradation tank 5.
Because the organic polluted water of the refractory organic matters often contains chloride ions, the method of the invention fully utilizes the chloride ions.
Injecting organic polluted water containing refractory organics into a degradation pool.
And measuring the concentration of the chloride ions in the organic polluted water by using an instrument such as a chloride ion concentration meter, and when the concentration of the chloride ions in the organic polluted water is lower than 30mg/L, adjusting the concentration of the chloride ions in the organic polluted water to be not lower than 30mg/L by adding chloride salt. The chloride salt is selected from one or more of sodium chloride, magnesium chloride and potassium chloride. The refractory organic substances comprise PPCPs, pesticide residues, industrial chemicals and the like, and the industrial chemicals comprise organic solvents, dyes, phenols and the like.
The power supply is connected, because the rate of electrochemically generating active chlorine and the current density are in a certain direct proportion relationship, the current is required to be adjusted to control the generation rate of the active chlorine according to the water amount, the required active chlorine amount and the like, so that the current density I of the anode electrode and the cathode electrode is 0<I≤500mA/cm2At this time, an electric field is formed between the anode and the cathode to cause the chlorine-containing water to electrochemically react, and chlorine ions in the chlorine-containing water lose electrons on the surface of the anode to generate HClO and ClO-And Cl2Free chlorine of (a). In this process, part of the water is also ionized to generate hydroxyl radicals. Meanwhile, the UV light emitted by the UV lamp irradiates to enable free chlorine to further generate strong oxidizing substances including hydroxyl radicals and active chlorine, and the organic pollutants which are difficult to degrade in the chlorine-containing water are oxidized and degraded. The active chlorine includes Cl*、Cl2 *—And ClO*。
The retention time of the chlorine-containing water in the degradation tank is 0.5-180 minutes (min). The treated water is discharged from the water outlet.
The following examples further illustrate the performance of the process of the present invention. In the examples, the water samples to be treated are the same surface water, the pH value is 7.6, the conductivity is 296 mu S/cm, and the water sample is 700mL, wherein 100 mu g/L metoprolol (metoprolol), Cl is dissolved in the water sample-The concentration is 5.5-300 mg/L, Cl-The concentration was adjusted by adding different amounts of NaCl. Metoproll is a drug that is slowly removed by both UV irradiation and HClO oxidation.
Example 1
The initial chloride ion concentration in the water sample to be treated is 100 mg/L. Adding a water sample to be treated into a cylindrical reactor, vertically and parallelly inserting a DSA anode and a stainless steel cathode into the reactor to immerse the DSA anode and the stainless steel cathode in water, correspondingly connecting the electrodes with a direct current power supply, and simultaneously inserting a UV lamp for irradiation. The distance between the two electrodes is 1cm, and the distance between the UV lamp and the anode is 1 cm. Meanwhile, the reactor is placed on a magnetic stirrer, so that the treated water sample is uniformly mixed.
The DSA anode is a titanium ruthenium-iridium plated electrode with the size of 4cm multiplied by 12 cm; the size of the cathode stainless steel electrode is 4cm multiplied by 12 cm; energizing in a DC power supplyThe current at both ends of the cathode and the anode is 200mA, namely the current density is 4.2mA/cm2. The UV lamp is a 10W low-pressure mercury lamp.
The treatment time is about 3min, and the removal rate of metoprolol can reach 90%.
Example 2
In this embodiment, the magnitude of the cathode and anode currents in embodiment 1 is replaced by 400mA, i.e. the current density is 8.3mA/cm2。
The treatment time is about 2min, and the removal rate of metoprolol can reach 90%.
Example 3
In this example, the magnitude of the cathode and anode currents in example 1 was changed to 800mA, i.e., the current density was 16.7mA/cm2。
The treatment time is about 1.7min, and the removal rate of metoprolol can reach 90%.
Example 4
This example replaces the chloride ion concentration in example 2 with 30 mg/L.
The treatment time is about 2min, and the removal rate of metoprolol can reach 90%.
Example 5
This example replaces the chloride ion concentration of example 2 with 300 mg/L.
The treatment time is about 0.8min, and the removal rate of metoprolol can reach 90%.
As can be seen from the above examples, the electrochemical-UV/Chlorine (E-UV/Chlorine) method of the present invention has a significant treatment effect. FIG. 2 further shows a comparison of the treatment effects of several methods, and it is also concluded that the electrochemical-UV/Chlorine (E-UV/Chlorine) method of the present invention has a significantly better treatment effect than Electrolysis (Electrolysis) or UV irradiation (UV).
The electrochemical-UV composite treatment method is not only limited to the treatment of PPCPs, but also is suitable for treating various industrial chemical wastewater, pesticide residue, medical wastewater and the like which are difficult to degrade.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The method for electrochemical-UV composite treatment of refractory organics is characterized by comprising the following steps:
placing an electrode group comprising at least one pair of anode electrode and cathode electrode into a degradation pool, wherein the anode electrode and the cathode electrode are respectively connected with a power supply; the anode electrode is a chlorine evolution electrode;
disposing a UV lamp between and proximate to the anode electrode and the cathode electrode;
injecting organic polluted water containing refractory organic matters into a degradation pool, wherein the refractory organic matters comprise 100 mu g/L of metoprolol, and adjusting the concentration of chloride ions in the organic polluted water to be 30-300 mg/L;
connecting a power supply, so that an electric field is formed between the anode electrode and the cathode electrode, the chlorine-containing water is subjected to electrochemical reaction, and chlorine ions in the chlorine-containing water lose electrons on the surface of the anode electrode to generate free chlorine; irradiating UV light emitted by the UV lamp to enable free chlorine to further generate strong oxidizing substances including hydroxyl radicals and active chlorine, and oxidizing and degrading the refractory organic pollutants in the chlorine-containing water; the retention time of the chlorine-containing water in the degradation tank is 0.5-180 min.
2. The method for electrochemical-UV composite treatment of refractory organics as claimed in claim 1, wherein the organic contaminated water is adjusted in chloride ion concentration by adding chloride salt, wherein the chloride salt is selected from any one or more of sodium chloride, magnesium chloride and potassium chloride.
3. The method for electrochemical-UV combined treatment of refractory organics as claimed in claim 1, wherein the anode electrode and the cathode electrode are rod-shaped or sheet-shaped electrodes.
4. The electrochemical-UV composite treatment refractory of claim 1The method of the organic matter is characterized in that the current density I of the anode electrode and the cathode electrode is selected to be 0<I≤500mA/cm2。
5. The electrochemical-UV composite treatment method for refractory organics according to claim 1, characterized in that the UV lamp is arranged in a degradation tank and is immersed in the organic polluted water.
6. The method for electrochemical-UV combined treatment of refractory organics as claimed in claim 1, wherein the UV lamp is disposed outside the degradation tank near the wall of the degradation tank, and the wall of the degradation tank on which the UV lamp is disposed is made of a material that can transmit UV light.
7. The method for electrochemical-UV composite treatment of refractory organics according to claim 1, wherein the UV lamp is arranged above the degradation tank along the liquid level of the degradation tank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910967504.3A CN110759437B (en) | 2019-10-12 | 2019-10-12 | Method for electrochemical-UV composite treatment of refractory organic matters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910967504.3A CN110759437B (en) | 2019-10-12 | 2019-10-12 | Method for electrochemical-UV composite treatment of refractory organic matters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110759437A CN110759437A (en) | 2020-02-07 |
| CN110759437B true CN110759437B (en) | 2022-02-01 |
Family
ID=69331669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910967504.3A Active CN110759437B (en) | 2019-10-12 | 2019-10-12 | Method for electrochemical-UV composite treatment of refractory organic matters |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110759437B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111646539A (en) * | 2020-06-04 | 2020-09-11 | 浙江大学 | UVC-LED-DSA electrode coupled photoelectrochemistry oxidized ammonia nitrogen synergistic removal system |
| CN111977865A (en) * | 2020-06-30 | 2020-11-24 | 中山大学 | Ballast water treatment device for removing electrolytic coupling LED photocatalysis series-connection halogenated matters |
| CN111620493A (en) * | 2020-07-03 | 2020-09-04 | 中国农业科学院农业环境与可持续发展研究所 | Method and special equipment for removing antibiotic resistant bacteria and resistant genes in sewage |
| CN112429801A (en) * | 2020-09-30 | 2021-03-02 | 南昌航空大学 | Method for treating high-concentration organic wastewater by ultraviolet light in cooperation with electrochemical oxidation |
| CN112340905B (en) * | 2020-10-28 | 2023-08-11 | 苏州清初环境科技有限公司 | Method and device for multi-wavelength ultraviolet-electrochemical sectional treatment of wastewater |
| CN113023972A (en) * | 2021-03-12 | 2021-06-25 | 南通寰宇博新化工环保科技有限公司 | High-salt organic wastewater treatment method based on electrochemical coupling hydrogen peroxide |
| CN113060879A (en) * | 2021-03-30 | 2021-07-02 | 上海应用技术大学 | Method for removing fluoroquinolone antibiotics in water based on ultraviolet/chlorine dioxide |
| CN116573732A (en) * | 2023-06-16 | 2023-08-11 | 中国药科大学 | Method for removing ARB and ARGs in water by using UV irradiation coupling in-situ chlorine production technology |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1446760A (en) * | 2003-04-26 | 2003-10-08 | 清华大学 | Method for removing trace amount of organic matter by using ozone/ultraviolet-biological activity carbon |
| JP2008264668A (en) * | 2007-04-19 | 2008-11-06 | Unitika Ltd | Method and apparatus for electrolytic treatment of wastewater |
| CN101734750A (en) * | 2008-11-19 | 2010-06-16 | 中国科学院生态环境研究中心 | Method for performing electrochemical advanced treatment on landfill leachate based on ultraviolet reinforcement |
| CN102101708A (en) * | 2011-01-12 | 2011-06-22 | 中国科学院生态环境研究中心 | Method and device for treating cyanide-containing wastewater through photoelectrochemistry |
| CN102219328A (en) * | 2010-04-16 | 2011-10-19 | 中国科学院生态环境研究中心 | Photoelectric integrated reactor capable of deeply treating garbage leachate |
| CN105152429A (en) * | 2015-09-07 | 2015-12-16 | 清华大学 | Method for efficiently removing organic pollutants in industrial wastewater |
| CN207581431U (en) * | 2017-10-27 | 2018-07-06 | 深圳市憬泰晖科技有限公司 | A kind of ultraviolet excitation device based on electrochemical oxidation |
| KR20200064878A (en) * | 2018-11-29 | 2020-06-08 | 포항공과대학교 산학협력단 | Photoelectrochemical water treatment apparutus and water treatment method using the same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2003216098A1 (en) * | 2002-01-24 | 2003-09-02 | The C And M Group, Llc | Mediated electrochemical oxidation of destruction of sharps |
| US7294270B2 (en) * | 2003-05-16 | 2007-11-13 | Fujifilm Corporation | Method of treating photographic waste liquid |
| AU2009226102A1 (en) * | 2008-03-21 | 2009-09-24 | Aptwater, Inc. | Apparatus, systems, and methods for water treatment |
| US8398828B1 (en) * | 2012-01-06 | 2013-03-19 | AquaMost, Inc. | Apparatus and method for treating aqueous solutions and contaminants therein |
| GB2515324A (en) * | 2013-06-19 | 2014-12-24 | Ramsey Yousif Haddad | Electrolytic advance oxidation processes to treat wastewater, brackish and saline water without hydrogen evolution |
| CN104591336B (en) * | 2015-01-26 | 2016-08-17 | 重庆文理学院 | A kind of from containing the method reclaiming phosphorus fosfomycin waste water |
| CN106219687A (en) * | 2016-08-15 | 2016-12-14 | 浙江大学 | A kind of method of pollutant in photoelectrocatalysis reduction treatment water body |
| CN109574421A (en) * | 2019-01-31 | 2019-04-05 | 清华大学深圳研究生院 | A kind of reverse osmosis concentration enhanced water processing method and equipment |
-
2019
- 2019-10-12 CN CN201910967504.3A patent/CN110759437B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1446760A (en) * | 2003-04-26 | 2003-10-08 | 清华大学 | Method for removing trace amount of organic matter by using ozone/ultraviolet-biological activity carbon |
| JP2008264668A (en) * | 2007-04-19 | 2008-11-06 | Unitika Ltd | Method and apparatus for electrolytic treatment of wastewater |
| CN101734750A (en) * | 2008-11-19 | 2010-06-16 | 中国科学院生态环境研究中心 | Method for performing electrochemical advanced treatment on landfill leachate based on ultraviolet reinforcement |
| CN102219328A (en) * | 2010-04-16 | 2011-10-19 | 中国科学院生态环境研究中心 | Photoelectric integrated reactor capable of deeply treating garbage leachate |
| CN102101708A (en) * | 2011-01-12 | 2011-06-22 | 中国科学院生态环境研究中心 | Method and device for treating cyanide-containing wastewater through photoelectrochemistry |
| CN105152429A (en) * | 2015-09-07 | 2015-12-16 | 清华大学 | Method for efficiently removing organic pollutants in industrial wastewater |
| CN207581431U (en) * | 2017-10-27 | 2018-07-06 | 深圳市憬泰晖科技有限公司 | A kind of ultraviolet excitation device based on electrochemical oxidation |
| KR20200064878A (en) * | 2018-11-29 | 2020-06-08 | 포항공과대학교 산학협력단 | Photoelectrochemical water treatment apparutus and water treatment method using the same |
Non-Patent Citations (3)
| Title |
|---|
| Removal of micropollutants by an eletromically driven UV/chlorine process for decentralized water treatment;Yinqiao Zhang等;《Water Research》;20200701;第183卷;第1-12页 * |
| 新型过滤电催化臭氧化工艺消毒及去除新兴有机物性能研究;张银巧;《中国优秀硕士学位论文全文数据库-工程科技I辑》;20190515(第2019年第05期);第B027-637页 * |
| 电解与紫外协同去除工厂化养殖循环水中氨氮效果研究;吴照学等;《农业机械学报》;20160430;第47卷(第4期);第274-279页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110759437A (en) | 2020-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110759437B (en) | Method for electrochemical-UV composite treatment of refractory organic matters | |
| KR101026641B1 (en) | Non-degradable Waste Water Treatment Apparatus using Electrolysis and Photo-fenton Oxidation Process | |
| Drogui et al. | Oxidising and disinfecting by hydrogen peroxide produced in a two-electrode cell | |
| Cotillas et al. | Optimization of an integrated electrodisinfection/electrocoagulation process with Al bipolar electrodes for urban wastewater reclamation | |
| Tian et al. | Cyanide oxidation by singlet oxygen generated via reaction between H2O2 from cathodic reduction and OCl− from anodic oxidation | |
| US9963362B2 (en) | Method for electrochemical bromide and/or chloride removal | |
| de OS Santos et al. | Testing the role of electrode materials on the electro-Fenton and photoelectro-Fenton degradation of clopyralid | |
| Donoso et al. | Electrochemical and sonochemical advanced oxidation processes applied to tartrazine removal. Influence of operational conditions and aqueous matrix | |
| US20230129237A1 (en) | Water-processing electrochemical reactor | |
| JP2004143519A (en) | Water treatment method and water treatment device | |
| Isidro et al. | How to avoid the formation of hazardous chlorates and perchlorates during electro-disinfection with diamond anodes? | |
| Thiam et al. | A first pre‐pilot system for the combined treatment of dye pollutants by electrocoagulation/EAOPs | |
| US20050224369A1 (en) | Electrolytic cell | |
| JP6649988B2 (en) | Method for controlling the generation of halogen-containing by-products in drinking water treatment | |
| WO2005058761A1 (en) | Electrolytic cell for treating contamined water | |
| Aquino et al. | Removal of phthalic acid from aqueous solution using a photo-assisted electrochemical method | |
| KR102052039B1 (en) | Apparatus for purifying water based on electro-peroxone reaction | |
| CN112340905B (en) | Method and device for multi-wavelength ultraviolet-electrochemical sectional treatment of wastewater | |
| da Silva et al. | Electrochemical generation of ozone for application in environmental remediation | |
| JP2003126860A (en) | Method and apparatus for treatment of waste liquid or waste water | |
| Sierra-Sánchez et al. | Photo-electrooxidation treatment of Acetaminophen in aqueous solution using BDD-Fe and BDD-Cu systems | |
| JP7566867B2 (en) | Control of on-site electrochemical generation of hydrogen peroxide for controlling ultraviolet advanced oxidation processes. | |
| JP2003073876A (en) | Electrode for electrochemical treatment, electrochemical treatment method and electrochemical treatment apparatus | |
| Bonola et al. | Implications to enhance sulfamethoxazole degradation using statistical optimization of either active chlorine concentration or ORP in an electrochemical reactor | |
| JP2005013858A (en) | Method and apparatus for treating wastewater using high voltage pulses |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |