CN113060801A - Electrochemical device for treating cyanide-containing wastewater and preparation method and application thereof - Google Patents
Electrochemical device for treating cyanide-containing wastewater and preparation method and application thereof Download PDFInfo
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- CN113060801A CN113060801A CN202110334829.5A CN202110334829A CN113060801A CN 113060801 A CN113060801 A CN 113060801A CN 202110334829 A CN202110334829 A CN 202110334829A CN 113060801 A CN113060801 A CN 113060801A
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- cyanide
- tio
- containing wastewater
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- graphite felt
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- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000002351 wastewater Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 claims abstract description 60
- 239000002184 metal Substances 0.000 claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000010439 graphite Substances 0.000 claims abstract description 57
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 57
- 239000010949 copper Substances 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 10
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 10
- 229940043237 diethanolamine Drugs 0.000 claims description 10
- 238000005286 illumination Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 abstract description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052725 zinc Inorganic materials 0.000 abstract description 16
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 239000000499 gel Substances 0.000 description 11
- 239000002071 nanotube Substances 0.000 description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- LEKPFOXEZRZPGW-UHFFFAOYSA-N copper;dicyanide Chemical compound [Cu+2].N#[C-].N#[C-] LEKPFOXEZRZPGW-UHFFFAOYSA-N 0.000 description 2
- JEVCWSUVFOYBFI-UHFFFAOYSA-N cyanyl Chemical compound N#[C] JEVCWSUVFOYBFI-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910011208 Ti—N Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- -1 clays Chemical compound 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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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
-
- 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
- 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
- C02F1/46104—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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention belongs to the technical field of wastewater treatment, and particularly relates to an electrochemical device for treating cyanide-containing wastewater, and a preparation method and application thereof. The electrochemical device for treating cyanide-containing wastewater comprises a power supply, an anode, a cathode and a container, wherein the power supply is respectively connected with the anode and the cathode, the anode and the cathode are both arranged in the container, and the anode is coated with TiO2The cathode of the graphite felt is a metal sheet. In the invention, TiO is mixed with2Coating gel on porous graphite felt, calcining to obtain electrode, coating TiO2The graphite felt is used as an anode, the metal sheet is used as a cathode, an external power supply is built into an electrochemical device for treating the cyanide-containing wastewater, a new idea is provided for the treatment of the cyanide-containing wastewater,can recover metal zinc and copper while decomposing organic matters, and has high treatment efficiency.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to an electrochemical device for treating cyanide-containing wastewater, and a preparation method and application thereof.
Background
Cyanide is a highly toxic chemical and is commonly used in various industrial processes including electroplating, gold and silver extraction, coal processing, nylon production and smelting. Due to the widespread use of cyanide in industry, large quantities of cyanide ions are often generated in industrial waste water. Gold, silver and other metals are extracted from ores by cyanide, and these processes are considered to be the most productive processes of cyanide waste water. Cyanide can be present not only in these industrial waste waters as free ions (CN-) but also bound to metal ions due to its strong binding force to metals. When cyanide comes into contact with dissolved metal ions, metal-cyanide complexes are formed. Although the cyanidation method is effective in extracting gold and silver, metal substances such as copper and zinc are dissolved in the ore. Therefore, cyanide wastewater must be treated to minimize the risk to health and the environment.
In recent years, the environmental protection problem is more and more emphasized, and higher environmental protection requirements are put forward for enterprises. The alkaline chlorination process is a commonly used method for treating cyanide-containing wastewater at present, but the method has the defect of generating cyanogen gas. In addition, the process uses a large amount of caustic soda and sodium hypochlorite, which causes serious corrosion to pipelines and equipment. To date, particularly from the viewpoint of large-scale industrial application, there has been no method capable of satisfying the requirements of the conventional cyanide wastewater treatment process, and therefore, the development of a new process for treating a large amount of cyanide-containing wastewater is urgent. One of the effective methods for purifying water pollutants and other toxic substances is the photocatalytic process, and most photocatalysts are metal oxides of semiconductor materials. Many photocatalysts such as ZnO and WO have been synthesized3、CdS、ZrO2、SnO2、BiVO4、TiO2And the like, and has higher photocatalytic activity. TiO 22It is best known for its high photocatalytic activity, good photostability, nontoxicity, repeated use without loss of activityA photocatalyst. But nano TiO2The particles have small particle size and high surface energy, and are easy to agglomerate, so that the effective surface area is reduced, and the catalytic efficiency is further reduced. Mixing nanometer TiO2The carrier surface is loaded on the carrier surface, which is an effective method for improving the dispersity and increasing the specific surface area. Some porous materials are often used as supports, such as silica gel, alumina, zeolite molecular sieves, clays, activated carbon. The carrier can be TiO with stronger oxidation-reduction performance2Provides an environment with higher substrate concentration, and improves the photocatalytic efficiency by enriching degraded substrate molecules. Whether nano TiO is used alone2Or nano TiO2The carrier is supported on a carrier, and the carrier is present in a powder state in a solution, and the solution needs to be filtered, and the metal is adsorbed on the catalytic material, and the metal ions adsorbed on the material need to be resolved, so that the carrier can be used continuously.
Chinese patent CN 108675382A discloses a TiO-based material2Integrated catalytic system of nanotube photocatalyst and degradation treatment method thereof based on TiO2Integrated catalytic system of nanotube photocatalyst comprising TiO2Nanotube, visible light source or sunlight, electric catalytic unit, and oxygen pump; the electrocatalytic device is made of TiO2The nanotube is an anode, the fibrous graphite felt is a cathode, and the anode and the cathode are both inserted into the organic wastewater and are respectively connected to the anode and the cathode of the voltage-stabilized power supply; the visible light source or the sunlight correspondingly irradiates the anode; fe is added into the organic wastewater2+The oxygenation pump is located at the cathode. By reacting with TiO2Applying external bias to the nanotube to form an external electric field environment to form TiO2The combination of photocatalysis and electrocatalysis, and further introduces Fenton reaction to form TiO2The integrated catalytic system with the synergistic effect of the mutual coupling of the visible light catalytic reaction, the electrocatalytic reaction and the Fenton reaction of the nanotube greatly improves the degradation efficiency of toxic refractory organic pollutants. In the patent, Ti-N alloy sheet is taken as an anode, organic solution containing a boron source is taken as electrolyte to carry out electrochemical anodic oxidation reaction, and N and B are doped into TiO2Soaking the N, B co-doped titanium dioxide nanotube in PdCl2The PdO loaded N, B co-doped titanium dioxide nanotube photocatalyst is prepared by drying and calcining in the solution, the preparation process is complex, the economic cost is high, palladium is loaded on the surface of the titanium dioxide nanotube in a PdO form, and Fe is required to be added in the treatment process2+Oxidized into Fe by hydrogen peroxide3+And hydroxyl radicals, and can further oxidize and decompose organic substances.
At present, it is demanded to provide an electrochemical device for treating cyanide-containing wastewater, which can decompose organic substances and recover metals at the same time and has high treatment efficiency.
Disclosure of Invention
The invention aims to provide an electrochemical device for treating cyanide-containing wastewater, which has simple structure, convenient operation, high treatment efficiency and capability of simultaneously decomposing organic matters and recovering metals; the invention also provides a preparation method and application of the electrochemical device for treating the cyanide-containing wastewater.
The electrochemical device for treating cyanide-containing wastewater comprises a power supply, an anode, a cathode and a container, wherein the power supply is respectively connected with the anode and the cathode, the anode and the cathode are both arranged in the container, and the anode is coated with TiO2The cathode of the graphite felt is a metal sheet.
The metal sheet is a copper sheet or a platinum sheet.
The container is a cylindrical container.
The preparation method of the electrochemical device for treating cyanide-containing wastewater comprises the following steps:
(1) mixing butyl titanate, absolute ethyl alcohol and diethanol amine to obtain a first mixed solution; adding concentrated nitric acid into water to adjust the pH value to obtain a second mixed solution, dropwise adding the second mixed solution into the first mixed solution, stirring and aging to obtain TiO2Gelling;
(2) inserting graphite felt into TiO2Soaking in gel, pulling out at constant speed, drying, roasting, and coating for the first time; repeating the coating after cooling to obtain the coated TiO2The graphite felt of (4);
(3) will coat TiO2The graphite felt and the metal sheet are put into a container and coated with TiO2The graphite felt and the metal sheet are respectively connected with the anode and the cathode of a power supply to assemble the electrochemical device for treating the cyanide-containing wastewater.
The molar ratio of the butyl titanate, the water, the absolute ethyl alcohol, the diethanolamine to the concentrated nitric acid in the step (1) is 0.8-1:0.8-1:8-10:0.8-1: 0.05-0.15.
The pH value in the step (1) is 2.5-3.5.
The dropping speed in the step (1) is 1-5 drops/second.
The stirring time in the step (1) is 0.5-2 h.
The aging described in the step (1) is aging in air.
The aging time in the step (1) is 24-36 hours.
The dipping time in the step (2) is 10-30 min.
The constant pulling speed in the step (2) is 1-3mm per second.
The graphite felt in the step (2) has the width of 1.5cm, the height of 12cm and the thickness of 3 mm.
The graphite felt in the step (2) is a hard graphite felt.
The roasting temperature in the step (2) is 350-500 ℃.
The repetition times in the step (2) are 3-9 times.
The electrochemical device for treating cyanide-containing wastewater is applied by firstly placing cyanide-containing wastewater in a container and then coating TiO2The graphite felt and the metal sheet are inserted into the cyanide-containing wastewater and coated with TiO2The graphite felt and the metal sheet are respectively connected with the anode and the cathode of a power supply, and finally, the graphite felt and the metal sheet are electrified under the illumination condition, so that the graphite felt and the metal sheet are obtained.
The voltage of the power supply is 10-30V.
The electrifying time is 2-7 hours.
The illumination condition is visible light illumination or ultraviolet light illumination, the light wavelength is 365-.
The electrochemical device for treating the cyanide-containing wastewater is applied to placing the cyanide-containing wastewater in a cylindrical containerWill be coated with TiO2The graphite felt and the metal sheet are vertically put into a container and coated with TiO2The graphite felt and the metal sheet are parallel to each other and coated with TiO2The graphite felt and the metal sheet are respectively connected with a power supply anode and a power supply cathode, and the concentrations of cyanide and copper-zinc metal in the cyanide-containing wastewater are analyzed after the graphite felt and the metal sheet are electrified under the illumination condition, so that the treatment effect is calculated.
The cyanide concentration in the cyanide-containing wastewater is 1-100ppm, the copper concentration is 10-30ppm, and the zinc concentration is 10-30 ppm; the cylindrical container is a glass container with a diameter of 5cm and a height of 10 mm.
The coated TiO2The spacing between the graphite felt and the metal sheet was 2 cm.
In the invention, TiO is mixed with2Coating gel on porous graphite felt, calcining to obtain electrode, coating TiO2The graphite felt is used as an anode, the metal sheet is used as a cathode, and an external power supply is built into an electrochemical device for treating cyanide-containing wastewater, thereby providing a new idea for the treatment of the cyanide-containing wastewater.
The principle of the invention is as follows:
in the electrolytic process H2Decomposition of O will produce O2。TiO2After irradiation with light, TiO2The electrons in the valence band are excited into the conduction band to form negatively charged highly active electrons e-Simultaneously, a positively charged hole h is formed in the valence band+Electron-hole pairs are formed. Electronic quilt O2Trapped, changed to O2 -. The hole combines with the OH-to form OH. The electrons are separated from the holes, and the holes diffuse to the catalyst surface. CN in solution-、[Cu(CN)3]2-、[Zn(CN)4]2-Moves to the surface of the anode under the action of an electric field and oxidizes CN under the action of a cavity-Is CN, is further oxidized into CNO under the action of hydroxyl radical, [ Cu (CN)3]2Oxidation by cavitation of the end product to Cu2+With a cyano radical, [ Zn (CN) ]4]2Oxidation by holes to Zn2+And a cyano radical. CNO further oxidized to NO2、CO2、H2O。Cu2+、Zn2+Reduced to metal deposit at the cathode.
The anode reaction is as follows:
TiO2+Av→e-+A+
OH-+h+→OH·
CN-+h+→·CN
[Cu(CN)3]2-+h+→[Cu(CN)2]-+·CN
[Cu(CN)2]-+h+→Cu(CN)+·CN
Cu(CN)+2h+→Cu2++·CN
[Zn(CN)4]2-+4h+→Zn2++4·CN
CN·+2OH·→H2O+·OCN
·OCN+2·OH+O2→O-N-O+CO2+H2O
the cathode reaction is as follows:
Zn2++2e＝ZnCn2++2e＝Cu
the invention has the following beneficial effects:
the invention utilizes a gel sol method to prepare titanium gel, adopts a stretching method to coat the gel on the surface of a graphite felt, obtains an anode after calcination, and takes a metal sheet as a cathode. When the cyanide-containing wastewater is treated, oxygen does not need to be introduced, and the oxygen generated in the electrolytic process is utilized to directly capture the nano TiO in the illumination process2The generated photo-generated electrons prevent the photo-generated electrons from being combined with holes. The holes oxidize cyanide in the cyanide-containing wastewater to decompose the cyanide, so that copper ions and zinc ions are released, and meanwhile, under the action of electric field force, the copper ions and the zinc ions obtain electrons at the cathode and are deposited at the cathode in a metal form. The anode of the invention is preparedThe process is simple, the metal zinc and copper can be recovered while the organic matters are decomposed, and the treatment efficiency is high.
Drawings
Fig. 1 is a schematic diagram of the principle of the present invention.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
An electrochemical device for treating cyanide-containing wastewater comprises a power supply, an anode, a cathode and a container, wherein the power supply is respectively connected with the anode and the cathode, the anode and the cathode are both arranged in the container, and the anode is coated with TiO2The cathode of the graphite felt is a metal sheet.
The metal sheet is a copper sheet.
The container is a cylindrical container.
The preparation method of the electrochemical device for treating the cyanide-containing wastewater comprises the following steps:
(1) adding butyl titanate, absolute ethyl alcohol and diethanol amine into a flask, and stirring for 20min to obtain a first mixed solution; adding water into a beaker, adding concentrated nitric acid, and adjusting the pH value to 3 to obtain a second mixed solution; dripping the second mixed solution into the flask at the speed of 1 drop/s, stirring for 1h to obtain light yellow transparent sol, and aging for 2 days to obtain TiO2Gelling; the molar ratio of the butyl titanate, the water, the absolute ethyl alcohol, the diethanolamine to the concentrated nitric acid is 1:1:10:1: 0.08;
(2) inserting a hard graphite felt into the TiO2Soaking in gel for 30min, uniformly pulling out at a height of 2mm per second, drying, roasting at 400 deg.C in a muffle furnace, and coating for the first time; cooling and then inserting TiO2In the gel, carrying out secondary coating; the coating was repeated 5 times to obtain a coated TiO2The graphite felt of (4);
(3) will coat TiO2The graphite felt and the metal sheet are put into a container and coated with TiO2The graphite felt and the metal sheet are respectively connected with the anode and the cathode of a power supply to assemble the electrochemical device for treating the cyanide-containing wastewater.
The application of the electrochemical device for treating the cyanide-containing wastewater is that the cyanide-containing wastewater (the total cyanide concentration is 7)1ppm, copper concentration 26ppm and zinc concentration 14ppm) was placed in a cylindrical container and the coated TiO was again placed2The graphite felt and the metal sheet are inserted into the cyanide-containing wastewater and coated with TiO2The spacing between the graphite felt and the metal sheet was 2 cm. Coating TiO2The graphite felt and the metal sheet are respectively connected with an anode and a cathode of a power supply, the concentrations of cyanide and copper and zinc in the cyanide-containing wastewater are analyzed after the power supply is electrified for 5 hours under the irradiation of visible light, the removal rates of the cyanide, the copper and the zinc are respectively 92%, 97% and 95%, and the copper and the zinc are deposited on the copper sheet in a metal form.
Example 2
An electrochemical device for treating cyanide-containing wastewater comprises a power supply, an anode, a cathode and a container, wherein the power supply is respectively connected with the anode and the cathode, the anode and the cathode are both arranged in the container, and the anode is coated with TiO2The cathode of the graphite felt is a metal sheet.
The metal sheet is a copper sheet.
The container is a cylindrical container.
The preparation method of the electrochemical device for treating the cyanide-containing wastewater comprises the following steps:
(1) adding butyl titanate, absolute ethyl alcohol and diethanol amine into a flask, and stirring for 20min to obtain a first mixed solution; adding water into a beaker, adding concentrated nitric acid, and adjusting the pH value to 3 to obtain a second mixed solution; dripping the second mixed solution into the flask at the speed of 2 drops/s, stirring for 2 hours to obtain light yellow transparent sol, and aging for 2 days to obtain TiO2Gelling; the molar ratio of the butyl titanate, the water, the absolute ethyl alcohol, the diethanol amine and the concentrated nitric acid is 0.8: 0.8: 8: 0.8: 0.05;
(2) inserting a hard graphite felt into the TiO2Soaking in gel for 30min, uniformly pulling out at a height of 1mm per second, drying, roasting at 500 deg.C in a muffle furnace, and coating for the first time; cooling and then inserting TiO2In the gel, carrying out secondary coating; the coating was repeated 5 times to obtain a coated TiO2The graphite felt of (4);
(3) will coat TiO2The graphite felt and the metal sheet are put into a container and coated with TiO2The graphite felt and the metal sheet are respectively connected with the anode and the cathode of a power supply to be assembled for useAn electrochemical device for treating cyanide-containing wastewater.
The electrochemical device for treating cyanide-containing waste water is applied by firstly placing cyanide-containing waste water (total cyanide concentration 71ppm, copper concentration 26ppm and zinc concentration 14ppm) in a cylindrical container and then coating TiO2The graphite felt and the metal sheet are inserted into the cyanide-containing wastewater and coated with TiO2The spacing between the graphite felt and the metal sheet was 2 cm. Coating TiO2The graphite felt and the metal sheet are respectively connected with an anode and a cathode of a power supply, the concentrations of cyanide and copper and zinc in the cyanide-containing wastewater are analyzed after the anode and the cathode are electrified for 7 hours under the irradiation of ultraviolet light, the removal rates of the cyanide, the copper and the zinc are respectively 94.5%, 98% and 99%, and the copper and the zinc are deposited on the copper sheet in a metal form.
Example 3
An electrochemical device for treating cyanide-containing wastewater comprises a power supply, an anode, a cathode and a container, wherein the power supply is respectively connected with the anode and the cathode, the anode and the cathode are both arranged in the container, and the anode is coated with TiO2The cathode of the graphite felt is a metal sheet.
The metal sheet is a copper sheet.
The container is a cylindrical container.
The preparation method of the electrochemical device for treating the cyanide-containing wastewater comprises the following steps:
(1) adding butyl titanate, absolute ethyl alcohol and diethanol amine into a flask, and stirring for 20min to obtain a first mixed solution; adding water into a beaker, and adding concentrated nitric acid to adjust the pH value to 3.5 to obtain a second mixed solution; dripping the second mixed solution into the flask at the speed of 3 drops/s, stirring for 1h to obtain light yellow transparent sol, and aging for 2.5 days to obtain TiO2Gelling; the molar ratio of the butyl titanate, the water, the absolute ethyl alcohol, the diethanol amine and the concentrated nitric acid is 1:1:10:1: 0.15;
(2) inserting a hard graphite felt into the TiO2Soaking in gel for 20min, uniformly pulling out at a height of 3mm per second, drying, roasting in a muffle furnace at 350 deg.C, and coating for the first time; cooling and then inserting TiO2In the gel, carrying out secondary coating; the coating was repeated 5 times to obtain a coated TiO2The graphite felt of (4);
(3) will be provided withCoating TiO2The graphite felt and the metal sheet are put into a container and coated with TiO2The graphite felt and the metal sheet are respectively connected with the anode and the cathode of a power supply to assemble the electrochemical device for treating the cyanide-containing wastewater.
The electrochemical device for treating cyanide-containing waste water is applied by firstly placing cyanide-containing waste water (total cyanide concentration is 75ppm, copper concentration is 30ppm, and zinc concentration is 16ppm) in a cylindrical container and then coating TiO2The graphite felt and the metal sheet are inserted into the cyanide-containing wastewater and coated with TiO2The spacing between the graphite felt and the metal sheet was 2 cm. Coating TiO2The graphite felt and the metal sheet are respectively connected with an anode and a cathode of a power supply, the concentrations of cyanide and copper and zinc in the cyanide-containing wastewater are analyzed after the anode and the cathode are electrified for 7 hours under the irradiation of visible light, the removal rates of the cyanide, the copper and the zinc are respectively 98%, 99% and 100%, and the copper and the zinc are deposited on the copper sheet in a metal form.
Claims (10)
1. An electrochemical device for treating cyanide-containing wastewater comprises a power supply, an anode, a cathode and a container, and is characterized in that the power supply is respectively connected with the anode and the cathode, the anode and the cathode are both arranged in the container, and the anode is coated with TiO2The cathode of the graphite felt is a metal sheet.
2. The electrochemical device for treating cyanide-containing wastewater according to claim 1, wherein the metal sheet is a copper sheet or a platinum sheet.
3. A method for preparing an electrochemical device for treating cyanide-containing wastewater according to claim 1 or 2, characterized by comprising the steps of:
(1) mixing butyl titanate, absolute ethyl alcohol and diethanol amine to obtain a first mixed solution; adding concentrated nitric acid into water to adjust the pH value to obtain a second mixed solution, dropwise adding the second mixed solution into the first mixed solution, stirring and aging to obtain TiO2Gelling;
(2) inserting graphite felt into TiO2Soaking in gel, pulling out at constant speed, drying, roasting, and coating for the first time; repeating the coating after cooling to obtain a coatingCoated with TiO2The graphite felt of (4);
(3) will coat TiO2The graphite felt and the metal sheet are put into a container and coated with TiO2The graphite felt and the metal sheet are respectively connected with the anode and the cathode of a power supply to assemble the electrochemical device for treating the cyanide-containing wastewater.
4. The method of claim 3, wherein the molar ratio of butyl titanate, water, absolute ethanol, diethanolamine to concentrated nitric acid in step (1) is 0.8-1:0.8-1:8-10:0.8-1: 0.05-0.15.
5. The method for preparing an electrochemical device for the treatment of cyanide-containing wastewater according to claim 3, wherein the pH in the step (1) is 2.5 to 3.5.
6. The method for preparing an electrochemical device for the treatment of cyanide-containing wastewater according to claim 3, wherein the dropping speed in step (1) is 1-5 drops/sec, the stirring time is 0.5-2 hours, and the aging time is 24-36 hours.
7. The method for preparing an electrochemical device for treating cyanide-containing wastewater as claimed in claim 3, wherein the dipping time in step (2) is 10-30min, the constant pulling speed is 1-3mm per second, the calcination temperature is 350-500 ℃, and the repetition times are 3-9 times.
8. Use of an electrochemical device according to claim 1 or 2 for the treatment of cyanide-containing waste water, characterized in that the cyanide-containing waste water is first placed in a container and the TiO-coated water is then applied2The graphite felt and the metal sheet are inserted into the cyanide-containing wastewater and coated with TiO2The graphite felt and the metal sheet are respectively connected with the anode and the cathode of a power supply, and finally, the graphite felt and the metal sheet are electrified under the illumination condition, so that the graphite felt and the metal sheet are obtained.
9. The use of an electrochemical device according to claim 8 for the treatment of cyanide-containing wastewater, characterized in that the voltage of the power supply is 10-30V and the energization time is 2-7 hours.
10. The use of the electrochemical device for treating cyanide-containing wastewater as claimed in claim 8, wherein the illumination condition is visible light illumination or ultraviolet light illumination, the light wavelength is 365-.
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