CN113957460A - Method for synthesizing hydrogen peroxide based on alternating current electrolysis, device and application thereof - Google Patents
Method for synthesizing hydrogen peroxide based on alternating current electrolysis, device and application thereof Download PDFInfo
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 238000000034 method Methods 0.000 title claims abstract description 58
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 54
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 38
- 239000003792 electrolyte Substances 0.000 claims abstract description 58
- 239000001301 oxygen Substances 0.000 claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000010865 sewage Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 33
- 239000007789 gas Substances 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 238000005273 aeration Methods 0.000 claims description 11
- 238000009792 diffusion process Methods 0.000 claims description 10
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
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- 238000006555 catalytic reaction Methods 0.000 claims description 8
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- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
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- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 229910000566 Platinum-iridium alloy Inorganic materials 0.000 claims description 2
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 2
- HWLDNSXPUQTBOD-UHFFFAOYSA-N platinum-iridium alloy Chemical class [Ir].[Pt] HWLDNSXPUQTBOD-UHFFFAOYSA-N 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
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- 238000003786 synthesis reaction Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 208000005623 Carcinogenesis Diseases 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 208000031320 Teratogenesis Diseases 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
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- 231100000504 carcinogenesis Toxicity 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000002550 fecal effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 238000007726 management method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 208000035473 Communicable disease Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
-
- 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
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
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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
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a method for synthesizing hydrogen peroxide based on alternating current electrolysis, a device and application thereof.A water and a conductive auxiliary electrolyte are taken as electrolyte, and the current density, the power frequency and the waveform are controlled by an alternating current variable frequency power supply, so that an electrode plate can continuously convert an anode and a cathode; when the electrode plate is used as an anode, oxygen is generated on the surface of the electrode plate; when the electrode plate is changed into a cathode, the oxygen generated in the anode state or the oxygen introduced together with the outside is reduced to generate hydrogen peroxide. The device comprises an electrolytic bath, at least one group of electrode plates arranged in the electrolytic bath and an alternating current variable frequency power supply; the alternating current variable frequency power supply is electrically connected with the electrode plate. The method for synthesizing hydrogen peroxide has the advantages of environmental protection, safety, no need of noble metal anode, high electrolysis efficiency, low energy consumption and low cost, and can be used for sewage treatment and disinfection.
Description
Technical Field
The invention belongs to the technical field of electrochemical synthesis processes, and particularly relates to a method for synthesizing hydrogen peroxide based on alternating current electrolysis, and a device and application thereof.
Background
The hydrogen peroxide has both oxidizability and reducibility, and is widely applied to the fields of medical treatment, aerospace, wastewater treatment, electronic industry, chemical synthesis, fabric bleaching, food industry and the like. And the products after the hydrogen peroxide reaction are water and oxygen, so the hydrogen peroxide is known as a clean and environment-friendly chemical product. The hydrogen peroxide synthesis method mainly comprises an anthraquinone method, an electrolytic method, a hydrogen and oxygen direct synthesis method and an air (oxygen) cathode reduction method. But the traditional anthraquinone method hydrogen peroxide production process has environmental protection risk. The electrolysis method has high energy consumption, needs a noble metal anode and has high cost. The main problem of the direct hydrogen-oxygen synthesis method is that hydrogen and oxygen are easy to explode after being mixed, and inevitable potential safety hazards exist; and the catalyst needs noble metal palladium, the catalytic efficiency is not high, and the market application prospect is limited. The hydrogen peroxide is produced by air (oxygen) cathode reduction method, wherein alkaline electrolyte is placed in an electrolytic bath to reduce oxygen in the air at the cathode to produce hydrogen peroxide. The method has the advantages of simple production of hydrogen peroxide, low cost, no pollution, high energy consumption and low hydrogen peroxide concentration in the product.
The traditional sewage treatment process (i.e. biological method) has the following problems: (1) the system has the advantages of non-standard design, low efficiency, large occupied area and large implementation difficulty; (2) the management is complex, the influence by seasons is large, and the water outlet effect is unstable; (3) after treatment, organic excess sludge needs to be discharged, and the generated peculiar smell affects the surrounding environment. The electrolysis method is generally adopted for industrial wastewater which is not suitable for biological treatment, but has the defects of high cost, low electrolysis efficiency, large equipment investment and high operation cost, and the electrolysis anode adopts titanium-based coated noble metal, so that the cost is high and the service life is short.
In recent years, water-borne pathogenic bacteria are attracting more and more attention, and especially the pathogenic bacteria can be propagated in a water distribution network system, thereby threatening human health. The disinfection of drinking water is an effective way to remove pathogenic microorganisms in water, prevent the spread of water-mediated infectious diseases and ensure the sanitary and safe drinking water. At present, common tap water disinfection methods can be classified into physical disinfection technical methods and chemical disinfection methods.
The physical disinfection technique commonly used therein is ultraviolet disinfection. The ultraviolet disinfection technology is simple to apply, microorganisms in drinking water can be effectively inactivated under the conditions of low dosage and short retention time, but the requirement of ultraviolet disinfection on the quality of inlet water is high, the ultraviolet disinfection and sterilization capacity is related to the radiation time and intensity, and in addition, an ultraviolet lamp also needs to be regularly cleaned and replaced, has no continuous sterilization capacity and has the risks of regeneration and secondary pollution.
Commonly used chemical disinfection methods include chlorine, chlorine dioxide, chloramine, ozone disinfection. Chlorination disinfection has characteristics such as effectual and the expense is low, and chlorination disinfection mainly acts through hypochlorous acid, and chlorine gets into the aquatic and reacts and forms hypochlorous acid, permeates to the bacterium surface of negatively charged to penetrate the cell wall and get into inside the bacterium, destroys the bacterial enzyme system through the oxidation and makes the bacterium die. However, the chlorine disinfection method is easy to react with organic matters coexisting in water, such as Natural Organic Matters (NOMs), to generate Disinfection Byproducts (DBPs) such as halogenated alkanes and halogenated aromatic hydrocarbons, and the substances have high toxicity, have risks of carcinogenesis, teratogenesis and mutagenesis, and have great threat to human health.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for synthesizing hydrogen peroxide based on alternating current electrolysis, a device and application thereof.
The invention is implemented by the following technical scheme:
a method for synthesizing hydrogen peroxide based on alternating current electrolysis comprises the following steps: water and conductive auxiliary electrolyte are taken as electrolyte, and the current density, power frequency and waveform are controlled by the alternating current variable frequency power supply 3, so that the electrode plate 2 continuously carries out anode and cathode conversion; when the electrode plate 2 is used as an anode, oxygen is generated on the surface of the electrode plate 2; when the electrode plate 2 is changed from the anode to the cathode, the oxygen generated in the anode state or the oxygen introduced together with the outside is reduced to generate hydrogen peroxide.
The synthesis electrode reaction is as follows:
the electrode is in an anode state: 2H2O→O2+4H++4e-
2OH-→H2O+1/2O2+2e
The electrode is in a cathode state: o is2+2H++2e-→H2O2
Optionally, the current density is 1-100mA/cm2(ii) a The frequency of the variable-frequency alternating current power supply is 1-5000Hz, and the waveform comprises sine waves, square waves or triangular waves.
Optionally, the electrode plate 2 is one of a gas diffusion electrode, an activated carbon fiber electrode, a carbon fiber cloth electrode, a graphite electrode, a platinum-iridium alloy electrode, a carbon steel electrode, a stainless steel electrode, an aluminum electrode, a lead dioxide electrode, a carbon nanotube electrode, or a graphene electrode.
Optionally, the conductive auxiliary electrolyte includes one or any combination of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium metasilicate, potassium sulfate, or sodium sulfate, and the mass concentration of the conductive auxiliary electrolyte is 0.01% to 15%.
The device manufactured according to the method for synthesizing hydrogen peroxide based on alternating current electrolysis comprises an electrolytic cell 1, at least one group of electrode plates 2 arranged in the electrolytic cell 1 and an alternating current variable frequency power supply 3, wherein the alternating current variable frequency power supply 3 is electrically connected with the electrode plates 2.
Optionally, further comprising an air supply mechanism; the air supply mechanism comprises an air pump 4, an air delivery pipe 5 and an air flow meter 6; the air pump 4 is communicated with the inlet end of the air delivery pipe 5, the air delivery pipe 5 is provided with the gas flowmeter 6, and the outlet end of the air delivery pipe 5 is communicated with the electrolytic cell 1.
Optionally, a gas distribution chamber 8 is further arranged at the bottom of the electrolytic cell 1, the gas distribution chamber 8 is communicated with the air delivery pipe 5 through a branch pipe 9, and a valve 10 is arranged on the branch pipe 9; the top of the gas distribution chamber 8 is provided with a plurality of aeration holes 11, and the electrolytic tank 1 is communicated with the gas distribution chamber 8 through the aeration holes 11. The aeration in the electrolytic process can ensure that the electrolyte in the electrolytic tank 1 is uniformly mixed, can provide sufficient oxygen for the electrolyte and is beneficial to the generation of hydrogen peroxide.
Optionally, the electrolysis device also comprises an electromagnetic heating stirrer 7, and the electrolysis bath 1 is placed on the electromagnetic heating stirrer 7.
An application of a method for synthesizing hydrogen peroxide based on alternating current electrolysis in sewage treatment comprises the following steps: the sewage is used as electrolyte, the ultraviolet lamp tube 12 is added into the electrolyte, the hydrogen peroxide is synthesized according to the method, the hydrogen peroxide generates hydroxyl radicals under the catalysis of ultraviolet rays generated by the ultraviolet lamp tube 12, and the organic matters in the sewage are oxidized and degraded by utilizing the strong oxidizing property of the hydroxyl radicals.
An application of a method for synthesizing hydrogen peroxide based on alternating current electrolysis in water disinfection treatment comprises the following steps: one of the treated sewage, swimming pool water or tap water is taken as electrolyte, an ultraviolet lamp tube 12 is added into the electrolyte, hydrogen peroxide is synthesized according to the method, and the hydrogen peroxide generates hydroxyl radicals under the catalysis of ultraviolet rays generated by the ultraviolet lamp tube 12, so that the strong oxidizing property of the hydroxyl radicals is utilized to kill microorganisms in the water.
Compared with the prior art, the invention has the following beneficial effects:
1. aiming at the problems in the existing hydrogen peroxide synthesis technology, the invention provides a method for synthesizing hydrogen peroxide based on alternating current electrolysis, wherein an electrolysis power supply innovatively adopts a variable-frequency alternating current power supply, so that the efficiency of synthesizing hydrogen peroxide by electrolysis is greatly improved; the requirements on the material of the electrode plate are greatly reduced, a gas diffusion electrode, an activated carbon fiber electrode, a graphite electrode, a stainless steel electrode, an aluminum electrode, a carbon steel electrode and the like can be used, the requirements on the components of the electrolyte are reduced, only water and trace conductive auxiliary electrolyte are needed, and hydrogen peroxide can be synthesized through alternating current electrolysis, so that the method has the advantages of environmental protection, safety, no need of a noble metal anode, high electrolysis efficiency, low energy consumption and low cost;
2. aiming at the defects of the existing sewage treatment technology, the technology of synthesizing hydrogen peroxide based on alternating current electrolysis is applied to the treatment of sewage and garbage percolate, only electric energy is consumed in the whole operation process, no medicament or other input materials are required to be added, and no harmful substances are generated; the sludge production is less than 10% of the existing treatment mode, so that the sludge treatment difficulty is greatly reduced; the method has the advantages of broad spectrum (being suitable for high-concentration and high-difficulty sewage treatment), high efficiency, stable treatment, environmental protection, less sludge discharge, less occupied land, low operation cost, easy management, low cost and the like, and meets the requirements of clean water treatment technology;
3. the invention is applied to water disinfection treatment based on the technology of synthesizing hydrogen peroxide by alternating current electrolysis, hydroxyl free radicals (OH) generated by the hydrogen peroxide under the catalysis of ultraviolet rays have extremely high oxidation capacity, can kill all microorganisms in a broad spectrum, and the product is water and carbon dioxide, thereby solving the problems that the existing disinfection technology has risks of causing three factors (carcinogenesis, teratogenesis and mutation) and the purple light disinfection technology has no continuous sterilization capacity, regeneration and secondary pollution; no medicament is added in the disinfection process, no harmful substance is generated, and the disinfection method has the advantages of environmental protection, high efficiency and low cost.
Drawings
Fig. 1 is a schematic structural view of embodiment 1 of the present invention.
Fig. 2 is a schematic structural diagram of embodiment 2 of the present invention.
Fig. 3 is a schematic structural view of embodiments 3 and 4 of the present invention.
In the figure: 1. the device comprises an electrolytic cell, 2 electrode plates, 3 an alternating current variable frequency power supply, 4 an air pump, 5 an air delivery pipe, 6 an air flow meter, 7 an electromagnetic heating stirrer, 8 an air distribution chamber, 9 a branch pipe, 10 a valve, 11 an aeration hole and 12 an ultraviolet lamp tube.
Detailed Description
The invention is further illustrated by the following figures and examples, without however restricting the scope of the invention to these examples.
Example 1
As shown in fig. 1, the device for synthesizing hydrogen peroxide based on alternating current electrolysis comprises an electrolytic cell 1 and a group of electrode plates 2 arranged in the electrolytic cell 1, wherein electrolyte is arranged in the electrolytic cell 1, and the device further comprises an alternating current variable frequency power supply 3 and an air supply mechanism; the alternating current variable frequency power supply 3 is electrically connected with the electrode plate 2; the air supply mechanism comprises an air pump 4, an air delivery pipe 5 and a gas flowmeter 6, the air pump 4 is communicated with the inlet end of the air delivery pipe 5, the air delivery pipe 5 is provided with the gas flowmeter 6, and the gas flowmeter 6 is used for metering and displaying the flow of the passing gas; the outlet end of the air delivery pipe 5 is arranged in the electrolytic cell 1 and connected with the electrode plate 2. Air (oxygen) is pumped into the periphery of the electrode plate through the air pump and the air delivery pipe, and if the oxygen supply is sufficient, the electrode plate in the cathode state can absorb enough oxygen to generate hydrogen peroxide.
Wherein, the utility model also comprises an electromagnetic heating stirrer 7, and the electrolytic bath 1 is arranged on the electromagnetic heating stirrer 7. The electromagnetic heating stirrer has the functions of heating and stirring simultaneously, can ensure that the electrolyte in the electrolytic bath 1 is uniformly mixed, and has the function of controlling the temperature of the electrolyte.
The method for synthesizing hydrogen peroxide by using the device comprises the following steps: water and conductive auxiliary electrolyte are taken as electrolyte, and the current density, power frequency and waveform are controlled by the alternating current variable frequency power supply 3, so that the electrode plate 2 continuously carries out anode and cathode conversion; when the electrode plate 2 is used as an anode, oxygen is generated on the surface of the electrode plate 2; when the electrode plate 2 is changed from the anode to the cathode, the oxygen generated in the anode state and the oxygen introduced by the air pump 4 are reduced to generate hydrogen peroxide.
Wherein the electrode plate is a gas diffusion electrode, the power frequency is 528Hz, the power waveform is square wave, and the current density is 20mA/cm2The electrolytic voltage is 3.2V, and the area of a single air (oxygen) diffusion electrode is 100cm2The electrolyte is sodium sulfate with the mass fraction of 5%, the temperature of the electrolyte is controlled to be 35 ℃ by an electromagnetic heating stirrer, the electrolysis time is controlled to be 20 minutes, and the air flow is 50 ml/min. The electrolysis is carried out by the method, and the concentration of hydrogen peroxide in the electrolyte after the electrolysis is finished is 9.6 mmol/L.
In addition, when the device is used for synthesizing hydrogen peroxide, gas is usedThe body diffusion electrode can also be replaced by an activated carbon fiber electrode, a carbon fiber cloth electrode, a graphite electrode, a platinum-containing or iridium-containing electrode, a carbon steel electrode, a stainless steel electrode, an aluminum electrode, a lead dioxide electrode, a carbon nanotube electrode or a graphene electrode, and when other electrodes except the body diffusion electrode are used, aeration is needed. The power waveform may be a sine wave, a triangle wave, or the like, in addition to a square wave. The conductive auxiliary electrolyte can also be replaced by sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, calcium hydroxide or potassium sulfate, and the mass concentration is in the range of 0.01-15% according to different conductive auxiliary electrolytes. According to the actual situation, the electrolytic current density is generally 1-100mA/cm2Within the range, the frequency of the variable frequency ac power supply is typically 1-5000 Hz.
Example 2
As shown in fig. 2, the device for synthesizing hydrogen peroxide based on alternating current electrolysis comprises an electrolytic cell 1 and at least one group of electrode plates 2 arranged in the electrolytic cell 1, wherein electrolyte is arranged in the electrolytic cell 1, and the device further comprises an alternating current variable frequency power supply 3 and an air supply mechanism; the alternating current variable frequency power supply 3 is electrically connected with the electrode plate 2; the air supply mechanism comprises an air pump 4, an air delivery pipe 5 and a gas flowmeter 6, the air pump 4 is communicated with the inlet end of the air delivery pipe 5, the air delivery pipe 5 is provided with the gas flowmeter 6, and the gas flowmeter 6 is used for metering and displaying the flow of the passing gas; the outlet end of the air delivery pipe 5 is arranged in the electrolytic cell 1 and connected with the electrode plate 2. Air (oxygen) is pumped into the periphery of the electrode plate through the air pump and the air delivery pipe, and if the oxygen supply is sufficient, the electrode plate in the cathode state can absorb enough oxygen to generate hydrogen peroxide.
Wherein, the bottom of the electrolytic cell 1 is also provided with a gas distribution chamber 8, the gas distribution chamber 8 is communicated with the air delivery pipe 5 through a branch pipe 9, and the branch pipe 9 is provided with a valve 10; the top of the gas distribution chamber 8 is provided with a plurality of aeration holes 11, and the electrolytic tank 1 is communicated with the gas distribution chamber 8 through the aeration holes 11. The aeration in the electrolytic process can ensure that the electrolyte in the electrolytic tank 1 is uniformly mixed, can provide sufficient oxygen for the electrolyte and is beneficial to the generation of hydrogen peroxide.
The application of the method for synthesizing hydrogen peroxide based on alternating current electrolysis in sewage treatment specifically comprises the following steps: sewage is taken as electrolyte, an ultraviolet lamp tube 12 is added into the electrolyte, and the current density, the power frequency and the waveform are controlled by an alternating current variable frequency power supply 3, so that the electrode plate 2 continuously carries out anode and cathode conversion; when the electrode plate 2 is used as an anode, oxygen is generated on the surface of the electrode plate 2; when the electrode plate 2 is changed from the anode to the cathode, the oxygen generated in the anode state and the oxygen introduced by the air pump 4 are reduced to generate hydrogen peroxide. Under the catalysis of ultraviolet rays generated by the ultraviolet lamp tube 12, the hydrogen peroxide generates hydroxyl radicals, and organic matters in the sewage are oxidized and degraded by utilizing the strong oxidizing property of the hydroxyl radicals.
The hydroxyl free radical (. OH) has extremely high oxidation capacity, can oxidize organic matters to generate carbon dioxide and water or degrade complex organic matters into simple organic matters, complete the treatment of COD and BOD of the sewage and improve the B/C value (biodegradability) of the sewage. In addition, phosphorus in the sewage can be oxidized into orthophosphate radicals by hydroxyl free radicals (. OH), and can form precipitation separation with heavy metal ions in the sewage. Ammonia nitrogen in the sewage can be oxidized to nitrogen and removed on the surface of the electrode or oxidized to nitrogen by hydroxyl free radical (. OH). Nitrate nitrogen in the sewage can be reduced to nitrogen gas on the surface of the electrode for removal.
Wherein: the electrode plate is an activated carbon fiber cloth electrode, the power frequency is 5000Hz, the power waveform is square wave, and the current density is as follows: 100mA/cm2The electrolytic voltage is 51V, the electrode area of single activated carbon fiber cloth is as follows: 100cm2The electrolyte component is domestic sewage (wherein COD is 167mg/L), the electrolyte temperature is room temperature, the power of the ultraviolet lamp tube is 0.1W, the air flow is 100ml/min, the electrolysis time is 5 minutes, and the COD in the electrolyte is 96mg/L after the method. Therefore, the method for synthesizing hydrogen peroxide based on alternating current electrolysis can be used for treating sewage, and the COD content in the sewage is obviously reduced.
In addition, the activated carbon fiber cloth can be replaced by a carbon fiber cloth electrode, a gas diffusion electrode, a graphite electrode, a carbon steel electrode, a stainless steel electrode, an aluminum electrode, a lead dioxide electrode, a carbon nanotube electrode, a graphene electrode, or the like when sewage is treated, wherein aeration is not required when a gas diffusion electrode is used. Power supplyThe waveform may be a sine wave, a triangular wave, or the like, in addition to a square wave. According to the actual situation, the electrolytic current density is generally 1-100mA/cm2Within the range, the frequency of the variable frequency AC power supply is generally 1-5000Hz, and the configuration power of the ultraviolet lamp tube is 0.1-3KW/m3。
Example 3
As shown in fig. 3, the device for synthesizing hydrogen peroxide based on alternating current electrolysis comprises an electrolytic cell 1 and at least one group of electrode plates 2 arranged in the electrolytic cell 1, wherein electrolyte is arranged in the electrolytic cell 1, and the device further comprises an alternating current variable frequency power supply 3, and the alternating current variable frequency power supply 3 is electrically connected with the electrode plates 2.
The application of the method for synthesizing hydrogen peroxide based on alternating current electrolysis in water disinfection treatment specifically comprises the following steps: the treated domestic sewage is taken as electrolyte, a small amount of electrolyte in the sewage is taken as conductive auxiliary electrolyte, an ultraviolet lamp tube 12 is added into the electrolyte, and the current density, the power frequency and the waveform are controlled by an alternating current variable frequency power supply 3, so that the electrode plate 2 continuously carries out the conversion of an anode and a cathode; when the electrode plate 2 is used as an anode, oxygen is generated on the surface of the electrode plate 2; when the electrode plate 2 is changed from the anode to the cathode, the oxygen generated in the anode state and the dissolved oxygen from the air in the domestic sewage are reduced to generate hydrogen peroxide. Under the catalysis of the ultraviolet rays generated by the ultraviolet lamp tube 12, the hydrogen peroxide generates hydroxyl radicals, and the strong oxidizing property of the hydroxyl radicals is utilized to kill microorganisms in the water.
Wherein: the electrode plate is a stainless steel (201) electrode, the power frequency is 4Hz, the power waveform is triangular wave, and the current density is 1mA/cm2Electrolytic voltage is 3V, electrode area of single stainless steel (201): 100cm2And the electrolyte component is bacteria-containing water (treated domestic sewage), wherein the fecal coliform group: not less than 24000/L, the temperature of the electrolyte is room temperature, the electrolysis time is 2 minutes, the power of the ultraviolet lamp tube is 0.1W, and the irradiation is carried out for 2 seconds after the electrolysis is finished. The faecal coliform group in the electrolyte components is 100 per liter after the method. From the above results, it can be seen that the method for synthesizing hydrogen peroxide based on alternating current electrolysis can significantly reduce the content of fecal coliform in the treated domestic sewage, thereby illustrating that the method for synthesizing hydrogen peroxide based on alternating current electrolysisThe method of (3) can be used for water disinfection treatment.
Example 4
As shown in fig. 3, the device for synthesizing hydrogen peroxide based on alternating current electrolysis comprises an electrolytic cell 1 and at least one group of electrode plates 2 arranged in the electrolytic cell 1, wherein electrolyte is arranged in the electrolytic cell 1, and the device further comprises an alternating current variable frequency power supply 3, and the alternating current variable frequency power supply 3 is electrically connected with the electrode plates 2.
The application of the method for synthesizing hydrogen peroxide based on alternating current electrolysis in water disinfection treatment comprises the following steps: the method comprises the following steps of taking tap water which is not subjected to disinfection treatment as electrolyte, taking a small amount of electrolyte in the tap water which is not subjected to disinfection treatment as conductive auxiliary electrolyte, adding an ultraviolet lamp tube 12 into the electrolyte, and controlling current density, power frequency and waveform through an alternating current variable frequency power supply 3 to enable an electrode plate 2 to continuously convert an anode and a cathode; when the electrode plate 2 is used as an anode, oxygen is generated on the surface of the electrode plate 2; when the electrode plate 2 is changed from the anode to the cathode, hydrogen peroxide is generated by reducing oxygen generated in the anode state and dissolved oxygen from air in tap water. Under the catalysis of the ultraviolet rays generated by the ultraviolet lamp tube 12, the hydrogen peroxide generates hydroxyl radicals, and the strong oxidizing property of the hydroxyl radicals is utilized to kill microorganisms in the water.
Wherein: the electrode plate is a graphite electrode, the power frequency is 528Hz, the power waveform is a sine wave, and the current density is 33mA/cm2The electrolytic voltage is 6V, and the area of a single graphite electrode is 100cm2The electrolyte is water containing bacteria (running water without disinfection treatment), wherein the content of Escherichia coli is 1000CFU/ml, the temperature of the electrolyte is room temperature, the electrolysis time is 1 minute, the power of an ultraviolet lamp tube is 0.1W, and the irradiation is carried out for 2 seconds after the electrolysis is finished. The content of the escherichia coli in the electrolyte is less than or equal to 1CFU/ml after the method is adopted. From the above results, it can be seen that the method for synthesizing hydrogen peroxide based on alternating current electrolysis can significantly reduce the content of escherichia coli in non-sterilized tap water, thus demonstrating that the method for synthesizing hydrogen peroxide based on alternating current electrolysis can be used for water sterilization.
In addition, when water is disinfected, the graphite electrode and the stainless steel electrode can be used as a gas diffusion electrode and an activated carbon fiberElectrodes, carbon fiber cloth electrodes, carbon steel electrodes, aluminum electrodes, lead dioxide electrodes, carbon nanotube electrodes, graphene electrodes, or the like. The power waveform may be a square wave, etc. in addition to a triangular wave or a sine wave. According to the actual situation, the electrolytic current density is generally 1-100mA/cm2Within the range, the frequency of the variable frequency AC power supply is generally 1-5000Hz, and the configuration power of the ultraviolet lamp tube is 0.1-3KW/m3Within the range.
The invention can take various sewage, garbage percolate, treated sewage, tap water (drinking water), swimming pool water and the like needing to treat COD and BOD as electrolyte for alternating current electrolysis, generates hydrogen peroxide on site, and uses ultraviolet light generated by an ultraviolet lamp tube to catalyze the hydrogen peroxide to generate hydroxyl free radicals, thereby completing the degradation treatment of various sewage and garbage percolate. And the treated sewage, tap water (drinking water) and swimming pool water are disinfected.
Claims (10)
1. A method for synthesizing hydrogen peroxide based on alternating current electrolysis is characterized by comprising the following steps: water and conductive auxiliary electrolyte are taken as electrolyte, and the current density, the power frequency and the waveform are controlled by the alternating current variable frequency power supply (3), so that the electrode plate (2) continuously carries out anode and cathode conversion; when the electrode plate (2) is used as an anode, oxygen is generated on the surface of the electrode plate (2); when the electrode plate (2) is changed from the anode to the cathode, the oxygen generated in the anode state or the oxygen introduced together with the outside is reduced to generate hydrogen peroxide.
2. The method for synthesizing hydrogen peroxide based on alternating current electrolysis according to claim 1, which is characterized by comprising the following steps: the current density is 1-100mA/cm2(ii) a The frequency of the variable-frequency alternating current power supply is 1-5000Hz, and the waveform comprises sine waves, square waves or triangular waves.
3. The method for synthesizing hydrogen peroxide based on alternating current electrolysis according to claim 1, which is characterized by comprising the following steps: the electrode plate (2) is one of a gas diffusion electrode, an activated carbon fiber electrode, a carbon fiber cloth electrode, a graphite electrode, a platinum-iridium alloy electrode, a carbon steel electrode, a stainless steel electrode, an aluminum electrode, a lead dioxide electrode, a carbon nanotube electrode or a graphene electrode.
4. The method for synthesizing hydrogen peroxide based on alternating current electrolysis according to claim 1, which is characterized by comprising the following steps: the conductive auxiliary electrolyte comprises one or any combination of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium metasilicate, potassium sulfate or sodium sulfate, and the mass concentration of the conductive auxiliary electrolyte is 0.01-15%.
5. The device manufactured by the method for synthesizing hydrogen peroxide based on alternating current electrolysis according to claim 1 comprises an electrolytic cell (1) and at least one group of electrode plates (2) arranged in the electrolytic cell (1), and is characterized in that: the electrode plate is characterized by further comprising an alternating current variable frequency power supply (3), wherein the alternating current variable frequency power supply (3) is electrically connected with the electrode plate (2).
6. The device for synthesizing hydrogen peroxide based on alternating current electrolysis according to claim 5, characterized in that: still include air supply mechanism, air supply mechanism include air pump (4), air delivery pipe (5) and gas flowmeter (6), air pump (4) with the entry end intercommunication of air delivery pipe (5), air delivery pipe (5) on be provided with gas flowmeter (6), the exit end of air delivery pipe (5) with electrolysis trough (1) intercommunication.
7. The device for synthesizing hydrogen peroxide based on alternating current electrolysis according to claim 5, characterized in that: a gas distribution chamber (8) is also arranged at the bottom of the electrolytic cell (1), the gas distribution chamber (8) is communicated with the air conveying pipe (5) through a branch pipe (9), and a valve (10) is arranged on the branch pipe (9); the top of the gas distribution chamber (8) is provided with a plurality of aeration holes (11), and the electrolytic tank (1) is communicated with the gas distribution chamber (8) through the aeration holes (11).
8. The device for synthesizing hydrogen peroxide based on alternating current electrolysis according to claim 5, characterized in that: the electrolytic tank is characterized by further comprising an electromagnetic heating stirrer (7), wherein the electrolytic tank (1) is placed on the electromagnetic heating stirrer (7).
9. The application of the method for synthesizing hydrogen peroxide based on alternating current electrolysis in sewage treatment, which is disclosed by claim 1, is characterized in that: the sewage is used as electrolyte, an ultraviolet lamp tube (12) is added into the electrolyte, hydrogen peroxide is synthesized according to the method, and then the hydrogen peroxide generates hydroxyl radicals under the catalysis of ultraviolet rays generated by the ultraviolet lamp tube (12), and organic matters in the sewage are oxidized and degraded by utilizing the strong oxidizing property of the hydroxyl radicals.
10. The application of the method for synthesizing hydrogen peroxide based on alternating current electrolysis in water disinfection treatment, which is characterized by comprising the following steps: one of the treated sewage, swimming pool water or tap water is taken as electrolyte, an ultraviolet lamp tube (12) is added into the electrolyte, hydrogen peroxide is synthesized according to the method, and the hydrogen peroxide generates hydroxyl radicals under the catalysis of ultraviolet rays generated by the ultraviolet lamp tube (12), so that the strong oxidizing property of the hydroxyl radicals is utilized to kill microorganisms in the water.
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