CN115094462A - Chlorine dioxide gas generating device based on foamed titanium monatomic integral electrode - Google Patents
Chlorine dioxide gas generating device based on foamed titanium monatomic integral electrode Download PDFInfo
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- CN115094462A CN115094462A CN202210537098.9A CN202210537098A CN115094462A CN 115094462 A CN115094462 A CN 115094462A CN 202210537098 A CN202210537098 A CN 202210537098A CN 115094462 A CN115094462 A CN 115094462A
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 title claims abstract description 270
- 239000004155 Chlorine dioxide Substances 0.000 title claims abstract description 135
- 235000019398 chlorine dioxide Nutrition 0.000 title claims abstract description 135
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000010936 titanium Substances 0.000 title claims abstract description 59
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 59
- 238000004140 cleaning Methods 0.000 claims abstract description 46
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims abstract description 41
- 229960002218 sodium chlorite Drugs 0.000 claims abstract description 41
- 239000003792 electrolyte Substances 0.000 claims abstract description 35
- 238000003860 storage Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000001514 detection method Methods 0.000 claims abstract description 17
- 239000012528 membrane Substances 0.000 claims abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000006260 foam Substances 0.000 claims description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 10
- 150000003624 transition metals Chemical class 0.000 claims description 10
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 9
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 9
- 235000011151 potassium sulphates Nutrition 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 12
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229940077239 chlorous acid Drugs 0.000 abstract 2
- 238000007664 blowing Methods 0.000 abstract 1
- 238000006056 electrooxidation reaction Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 abstract 1
- 229910001919 chlorite Inorganic materials 0.000 description 24
- 229910052619 chlorite group Inorganic materials 0.000 description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 238000004659 sterilization and disinfection Methods 0.000 description 9
- 230000008859 change Effects 0.000 description 6
- 239000000645 desinfectant Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000001963 growth medium Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000003206 sterilizing agent Substances 0.000 description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 241000193830 Bacillus <bacterium> Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GLMGLOKOFVECMS-UHFFFAOYSA-K C(C)O.[Ru](Cl)(Cl)Cl Chemical compound C(C)O.[Ru](Cl)(Cl)Cl GLMGLOKOFVECMS-UHFFFAOYSA-K 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910001902 chlorine oxide Inorganic materials 0.000 description 1
- MAYPHUUCLRDEAZ-UHFFFAOYSA-N chlorine peroxide Chemical compound ClOOCl MAYPHUUCLRDEAZ-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000006806 disease prevention Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000006916 nutrient agar Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000011012 sanitization Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
-
- 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
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- 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
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
-
- 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
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
Abstract
The invention relates to a chlorine dioxide gas generating device based on a foamed titanium monatomic integral electrode. The device comprises an electrochemical reactor and a circulating feeding and cleaning device, wherein the electrochemical reactor comprises a cathode chamber, a cathode, a proton exchange membrane, an anode and an anode chamber, and the circulating feeding and cleaning device comprises a circulating buffer tank, a sodium chlorite concentration detection and flow control instrument, a raw material and cleaning solution storage tank and conveying equipment. Chlorous acid is continuously converted into chlorine dioxide at the position of the single-atom integral anode by utilizing an electrochemical oxidation technology, then the chlorine dioxide flows out by blowing air along with the bottom of the anode chamber, the concentration of the chlorous acid is detected in real time by utilizing a sodium chlorite concentration detection and flow control instrument in the electrolysis process, and the anode electrolyte replenishing and electrode surface cleaning modes are automatically switched as required. The invention can efficiently and continuously generate high-purity chlorine dioxide, has low energy consumption, high electrode activity and selectivity and no secondary pollution, and is suitable for industrial popularization.
Description
Technical Field
The invention relates to the technical field of preparation of disinfection reagents, in particular to a chlorine dioxide gas generating device based on a foamed titanium monatomic integral electrode.
Background
Currently, the fourth generation disinfectant chlorine dioxide, which is recognized by the world health organization as a class a1 broad-spectrum, safe, and highly effective disinfectant, has been widely used in a variety of fields including environmental disinfection, disease prevention, sewage treatment, and the like. However, the use of current chlorine dioxide sanitizing agents relies on-site preparation, since chlorine dioxide is extremely unstable and difficult to store and transport.
The current commercial preparation process of chlorine dioxide mainly comprises a chemical method and an electrolytic method. Chlorine dioxide generators based on chemical processes can generate chlorine dioxide by chemical reaction of hydrochloric acid and sodium chlorate. But the hydrochloric acid and the sodium chlorate raw material have potential safety hazards in the processes of storage, transportation and use. In addition, the process also has the problems of impure chlorine dioxide products, easy secondary pollution and the like. The chlorine dioxide generator based on the electrolytic method is used for preparing chlorine dioxide by electrochemically oxidizing or reducing sodium chlorate or sodium chlorite at an anode or a cathode, and has the defects of high electrode cost, impure products and the like at present. In addition, the electrode is easily polluted by impurities in the electrolyte in the process of continuously electrolyzing to prepare the chlorine dioxide, so that the activity and the selectivity of the electrode are reduced, and the continuous work of the generator is influenced. Therefore, the development of a novel chlorine dioxide generator which is cheap, safe, efficient and can continuously prepare high-purity chlorine dioxide is the key for popularization and application of the chlorine dioxide disinfection reagent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a chlorine dioxide gas generating device based on a foamed titanium monatomic integral electrode and an application method based on the device, and aims to continuously and efficiently generate high-purity chlorine dioxide gas.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a chlorine dioxide gas generating device based on a foamed titanium monatomic integral electrode, which can continuously and efficiently generate high-purity chlorine dioxide gas and comprises an electrochemical reactor and a circulating feeding and cleaning device, wherein the electrochemical reactor comprises a cathode chamber, a cathode, a proton exchange membrane, an anode and an anode chamber, the proton exchange membrane is arranged between the anode and the cathode, the cathode chamber, the cathode, the proton exchange membrane, the anode and the anode chamber are arranged and clamped,
the cathode and the anode are respectively connected with the cathode and the anode of a power supply through leads;
the circular feeding and cleaning device comprises a circular buffer tank, a sodium chlorite concentration detection and flow control instrument, a raw material storage tank, a cleaning solution storage tank and conveying equipment;
the circulating buffer tank is connected with the anode chamber through a pipeline, and electrolyte containing sodium chlorite is recycled; the circulating buffer tank is connected with the raw material storage tank and the cleaning liquid storage tank through pipelines, and the cleaning mode and the feeding mode are automatically switched through sodium chlorite concentration detection and a flow controller;
the anode is a foamed titanium monatomic integral electrode, and the cathode is a porous foamed nickel electrode.
The anode of the invention adopts a foamed titanium monatomic integral electrode, and can efficiently and selectively oxidize the chlorite to be chlorine dioxide.
Therefore, it can be understood that in the technical scheme of the invention, as the anode adopts the titanium foam-based monatomic integral electrode, the chlorite can be efficiently and highly selectively converted into chlorine dioxide, the chlorine dioxide is pumped into the air along with the bottom of the anode chamber to be discharged, and in the continuous electrolysis process, the sodium chlorite concentration detection and flow control instrument connected with the raw material storage tank and the cleaning solution storage tank can automatically switch the cleaning mode and the feeding mode according to the chlorite concentration in the circulating buffer tank, so that the activity of the electrode and the chlorite concentration in the electrolyte are maintained, and the continuous generation of high-purity chlorine dioxide is ensured. Therefore, the chlorine dioxide gas generating device based on the foamed titanium monoatomic integrated electrode can realize the continuous selective oxidation from the chlorite to the chlorine dioxide and realize the efficient and continuous generation of the high-purity chlorine dioxide. And the foamed titanium-based metal monatomic integral electrode has higher activity and better stability, and is beneficial to improving the selectivity of converting the chlorite into chlorine dioxide. And a circulating feeding and cleaning device is arranged, so that the high-purity chlorine dioxide can be ensured to be continuously generated for a long time.
In the invention, the electrochemical reactor is matched with a circulating feeding and cleaning device to realize electrode surface cleaning and anolyte replenishment and ensure the continuous generation of high-purity chlorine dioxide; the automatic liquid inlet and gas inlet system consists of a pressurization controller and a flow controller, and stably controls the circulation of the electrolyte and the flow rate of the discharged chlorine dioxide gas.
In one embodiment of the invention, the anode chamber and the cathode chamber are both made of insulating materials and are tightly attached to the electrodes and the proton exchange membrane, so that the sealing effect of the device is ensured to be leak-free.
In one embodiment of the present invention, the titanium foam monatomic bulk electrode uses titanium foam as a substrate, and forms a transition metal monatomic or nanocluster active material on the surface of the titanium foam by using a process such as spraying or pyrolysis.
In one embodiment of the present invention, for the titanium foam monatomic bulk electrode, the transition metal monatomic is at least one of manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold.
In one embodiment of the invention, the mass loading of the transition metal monoatomic species on the titanium foam monoatomic monolith electrode is in the range of 0.01% to 20%.
In one embodiment of the invention, the titanium foam monatomic bulk electrode is a porous structure with micropores ranging in pore size from 50 to 100 microns, and is used for gas diffusion.
In one embodiment of the invention, in the chlorine dioxide gas generating device based on the foamed titanium monatomic integrated electrode, the anolyte is sodium chlorite electrolyte; the cathode electrolyte is sodium sulfate or potassium sulfate solution; the cleaning solution is deionized water.
In one embodiment of the invention, the anolyte or catholyte concentration ranges from 0.1mol/L to 5 mol/L.
In one embodiment of the invention, the delivery device is a fan or an air pump or a water pump.
In a second aspect of the present invention, there is provided a method for applying the titanium foam monatomic integrated electrode-based chlorine dioxide gas generating device according to the first aspect of the present invention, wherein the titanium foam monatomic integrated electrode-based chlorine dioxide gas generating device is used for continuously preparing high-purity chlorine dioxide gas, and the method comprises the following steps:
introducing electrolyte containing sodium chlorite into an anode chamber, introducing air into the anode chamber, introducing potassium sulfate or sodium sulfate electrolyte into a cathode chamber, introducing the electrolyte containing sodium chlorite from the bottom of the anode at a certain flow rate, flowing through the anode, and finally discharging from the upper end of the anode chamber; in the process, a voltage is applied between the cathode and the anode, sodium chlorite in the electrolyte is selectively converted into chlorine dioxide on the surface of the anode, and the generated chlorine dioxide flows out along with air pumped in the bottom of the anode.
In one embodiment of the present invention, a constant voltage of 0.5V to 36V or a constant current of 0.1 to 50A is applied between the anode and the cathode, and the flow rate of the gas is controlled to be in the range of 0.001m/s to 10m/s and the flow rate of the electrolyte is controlled to be in the range of 1mL/min to 500 mL/min.
In one embodiment of the invention, during continuous electrolysis, a sodium chlorite concentration detection and flow control instrument is used to detect the chlorite concentration in real time and switch the electrode surface cleaning and anolyte replenishment modes as required.
In one embodiment of the invention, the prepared chlorine dioxide gas can be used as a chlorine dioxide disinfectant and is used in the fields of disinfection, sterilization, environmental protection and the like.
Compared with the prior art, according to the technical scheme, the anode adopts the foamed titanium-based integral electrode loaded with metal monoatomic atoms, hypochlorite can be selectively oxidized into chlorine dioxide at the anode, then high-purity chlorine dioxide continuously flows out along with air pumped in from the bottom of the anode, the concentration of the chlorite is detected in real time by using a sodium chlorite concentration detection and flow control instrument, and the functions of anode electrolyte supplement and electrode surface cleaning are switched as required, so that the efficient and continuous generation of the chlorine dioxide is ensured. Therefore, the chlorine dioxide gas generating device based on the foamed titanium monoatomic integrated electrode can realize the continuous selective oxidation from the chlorite to the chlorine dioxide and realize the efficient and continuous generation of the high-purity chlorine dioxide. And the foamed titanium-based metal single-atom integral electrode has higher activity and better stability, and is beneficial to improving the selectivity of converting chlorite into chlorine dioxide. And a circulating feeding and cleaning device is arranged, so that high-purity chlorine dioxide can be prevented from being continuously generated for a long time. The device of the invention is used for generating chlorine dioxide gas, has low energy consumption, high electrode activity and selectivity, can efficiently and continuously generate high-purity chlorine dioxide, has no secondary pollution, and is suitable for industrial popularization.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a chlorine dioxide gas generating device based on a foamed titanium single-atom integral electrode in the embodiment.
FIG. 2 is a schematic diagram of a Ti-foam-based ruthenium monatomic bulk electrode.
FIG. 3 is an AC-TEM image of a Ti-foam based ruthenium monatomic bulk electrode.
FIG. 4 is a diagram of the selectivity of chlorine dioxide generated by electrolyzing chlorite by using a titanium foam-based ruthenium monatomic integral electrode.
FIG. 5 is a graph showing the change of chlorine dioxide concentration and voltage during the long-time electrolysis of chlorite by using foamed titanium-based ruthenium monatomic integrated electrode.
FIG. 6 is a graph showing the change in concentration of chlorine dioxide produced by electrolyzing chlorite using the apparatus before and after cleaning the electrode.
Fig. 7 is a graph showing the change of formaldehyde concentration in air with time during the operation of the chlorine dioxide generator.
Fig. 8 is a graph showing the air sterilization effect of the chlorine dioxide generation device.
As indicated by the reference numbers in fig. 1: 1. the device comprises a cathode chamber, a cathode, a proton exchange membrane 3, a proton exchange membrane 4, an anode 5, an anode chamber 6, a circulating buffer tank 7, a sodium chlorite concentration detection and flow control instrument 8, conveying equipment 9, a raw material storage tank 10 and a cleaning solution storage tank.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
Referring to fig. 1, the first aspect of the present invention provides a chlorine dioxide gas generating device based on a titanium foam monatomic monolithic electrode, which can continuously and efficiently generate high-purity chlorine dioxide gas, comprising an electrochemical reactor, a circulating feeding and cleaning device, wherein the electrochemical reactor comprises a cathode chamber 1, a cathode 2, a proton exchange membrane 3, an anode 4 and an anode chamber 5, the proton exchange membrane 3 is arranged between the anode 4 and the cathode 2, the cathode chamber 1, the cathode 2, the proton exchange membrane 3, the anode 4 and the anode chamber 5 are clamped in an arrangement,
the cathode 2 and the anode 4 are respectively connected with the cathode and the anode of a power supply through leads;
the circular feeding and cleaning device comprises a circular buffer tank 6, a sodium chlorite concentration detection and flow control instrument 7, a raw material storage tank 9, a cleaning solution storage tank 10 and conveying equipment 8;
the circulating buffer tank 6 is connected with the anode chamber 5 through a pipeline, and electrolyte containing sodium chlorite is recycled; the circulating buffer tank 6 is connected with the raw material storage tank 9 and the cleaning liquid storage tank 10 through pipelines, and the cleaning mode and the feeding mode are automatically switched through the sodium chlorite concentration detection and flow control instrument 7;
the anode 4 is a foamed titanium monatomic integral electrode, and the cathode 2 is a porous foamed nickel electrode.
The anode of the invention adopts a foamed titanium monatomic integral electrode, and can efficiently and selectively oxidize the chlorite to be chlorine dioxide.
Therefore, it can be understood that, in the technical scheme of the invention, because the anode 4 adopts the titanium foam based monatomic integrated electrode, the chlorite can be efficiently and selectively converted into chlorine dioxide, the chlorine dioxide is pumped into the air along with the bottom of the anode chamber 5 to be discharged, and in the continuous electrolysis process, the sodium chlorite concentration detection and flow control instrument 7 connected with the raw material storage tank 9 and the cleaning solution storage tank 10 can automatically switch the cleaning mode and the feeding mode according to the chlorite concentration in the circulating buffer tank 6, so that the activity of the electrode and the chlorite concentration in the electrolyte are maintained, and the continuous generation of high-purity chlorine dioxide is ensured. Therefore, the chlorine dioxide gas generating device based on the foamed titanium monoatomic integrated electrode can realize the continuous selective oxidation from the chlorite to the chlorine dioxide and realize the efficient and continuous generation of the high-purity chlorine dioxide. And the foamed titanium-based metal monatomic integral electrode has higher activity and better stability, and is beneficial to improving the selectivity of converting the chlorite into chlorine dioxide. And a circulating feeding and cleaning device is arranged, so that the high-purity chlorine dioxide can be ensured to be continuously generated for a long time.
In the invention, the electrochemical reactor is matched with a circulating feeding and cleaning device to realize electrode surface cleaning and anolyte replenishment and ensure the continuous generation of high-purity chlorine dioxide; the automatic liquid inlet and gas inlet system consists of a pressurization controller and a flow controller, and stably controls the circulation of the electrolyte and the flow rate of the discharged chlorine dioxide gas.
In addition, it should be noted that the chlorine dioxide gas generating device based on the titanium foam monatomic integrated electrode further comprises a conveying pipeline, wherein the conveying pipeline is communicated with the cathode chamber 1 and the anode chamber 5, the anode chamber 5 is communicated with the circulation buffer tank 6, the circulation buffer tank 6 is communicated with the raw material storage tank 9 and the cleaning solution storage tank 10 through the conveying pipeline, conveying equipment 8 is arranged on the conveying pipeline, and the conveying equipment 8 is a fan or an air pump or a water pump.
In one embodiment of the invention, the anode chamber and the cathode chamber are both made of insulating materials and are tightly attached to the electrodes and the proton exchange membrane, so that the sealing effect of the device is ensured to be leak-free.
In one embodiment of the present invention, the titanium foam monatomic bulk electrode uses titanium foam as a substrate, and forms a transition metal monatomic or nanocluster active material on the surface of the titanium foam by using a process such as spraying or pyrolysis.
In one embodiment of the present invention, for the titanium foam monatomic bulk electrode, the transition metal monatomic is at least one of manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold. The manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum and gold monatomic can be used as the active component of the anode 4 for realizing the selective oxidation of chlorite into chlorine dioxide, and one or more of the components can be selected when in use.
In one embodiment of the invention, the mass loading of the transition metal monoatomic species on the titanium foam monoatomic monolith electrode is in the range of 0.01% to 20%. For example, the transition metal monoatomic amount is 0.01%, 0.1%, 1%, 5%, 10%, or 20%. Preferably, the loading is 0.1% to 1%, such as 0.1%, 0.2%, 0.4%, 0.8% or 1%.
In one embodiment of the invention, the titanium foam monatomic bulk electrode is of a porous structure with micropores ranging in size from 50 to 100 microns, and is used for gas diffusion.
In one embodiment of the invention, in the chlorine dioxide gas generating device based on the foamed titanium monatomic integrated electrode, the anolyte is sodium chlorite electrolyte; the catholyte is solution of sodium sulfate or potassium sulfate, etc.; the cleaning solution is deionized water.
In one embodiment of the invention, the anolyte or catholyte concentration ranges from 0.1mol/L to 5 mol/L. Preferably, the concentration is 0.5-2.5mol/L, such as 0.5, 1, 1.5, 2, 2.5 mol/L.
In a second aspect of the present invention, there is provided a method for applying the titanium foam monatomic integrated electrode-based chlorine dioxide gas generating device according to the first aspect of the present invention, wherein the titanium foam monatomic integrated electrode-based chlorine dioxide gas generating device is used for continuously preparing high-purity chlorine dioxide gas, and comprises the following steps:
introducing electrolyte containing sodium chlorite into an anode chamber, introducing air into the anode chamber, introducing potassium sulfate or sodium sulfate electrolyte into a cathode chamber, introducing the electrolyte containing sodium chlorite from the bottom of the anode at a certain flow rate, flowing through the anode, and finally discharging from the upper end of the anode chamber; in the process, a voltage is applied between the cathode and the anode, sodium chlorite in the electrolyte is selectively converted into chlorine dioxide on the surface of the anode, and the generated chlorine dioxide flows out along with air pumped in the bottom of the anode.
In one embodiment of the present invention, a constant voltage of 0.5V to 36V or a constant current of 0.1 to 50A is applied between the anode and the cathode, and the flow rate of the gas is controlled to be in the range of 0.001m/s to 10m/s and the flow rate of the electrolyte is controlled to be in the range of 1mL/min to 500 mL/min.
The voltage range here is preferably 2V-5V, for example 2V, 3V, 4V or 5V. The chlorite is efficiently and selectively oxidized into chlorine dioxide by adjusting the voltage.
The voltage range here is preferably 1A-5A, for example with an applied current of 1A, 2A, 3A, 4A or 5A. The chlorite is efficiently and selectively oxidized into chlorine dioxide by adjusting the current.
The flow rate of air here is preferably in the range from 1 to 5m/s, for example, a flow rate of 1m/s, 2m/s, 3m/s, 4m/s or 5m/s is employed. The flow rate of air pumped into the bottom of the anode is adjusted to make most of the chlorine dioxide in the anolyte be utilized.
The flow rate of the electrolyte here is preferably in the range from 50 to 250mL/min, for example with a flow rate of 50mL/min, 100mL/min, 150mL/min, 200mL/min or 250 mL/min. The rate of conversion of chlorite to chlorine dioxide in the electrochemical reactor is increased by adjusting the electrolyte flow rate.
In one embodiment of the invention, during continuous electrolysis, the sodium chlorite concentration is detected in real time by a sodium chlorite concentration detection and flow control instrument and the electrode surface cleaning and anolyte replenishing modes are switched as required.
In one embodiment of the invention, the prepared chlorine dioxide gas can be used as a chlorine dioxide disinfectant and is used in the fields of sterilization, environmental protection and the like.
The method and the device for continuously and efficiently generating the chlorine dioxide disinfectant agent are described in detail by specific embodiments.
Example 1:
(1) preparation of the anode 4: dissolving 20mg of ruthenium chloride in 5mL of ethanol, spraying the ruthenium chloride ethanol solution on a porous titanium foam surface of 2cm (length) by 2cm (width) by 0.68cm (thickness), and finally spraying the solution on H 2 And calcining the titanium foam-based ruthenium monatomic integral anode 4 at 400 ℃ in the Ar atmosphere. A physical image and an AC-TEM image of the ruthenium monoatomic anode 4 are shown in FIGS. 2 and 3.
(2) Assembling a high-purity chlorine dioxide continuous generating device: and (2) taking the electrode prepared in the step (1) as an anode 4, taking foamed nickel as a cathode 2, then clamping the cathode chamber 1, the cathode 2, the proton exchange membrane 3, the anode 4 and the anode chamber 5, and simultaneously respectively connecting the cathode 2 and the anode 4 with a negative electrode and a positive electrode of a power supply through leads to obtain the electrochemical reactor. The circulation buffer tank 6 is connected to the anode chamber 4 of the electrochemical reactor by a pipe, and the circulation buffer tank 6 is connected to the raw material storage tank 9 and the cleaning solution storage tank 10 by a pipe.
(3) The method for preparing the chlorine dioxide sterilizing agent by using the high-purity chlorine dioxide continuous generation device in the step (2) comprises the following steps: electrolyte containing sodium chlorite is led into a circulating buffer tank 6 through a water pump 8, the sodium chlorite electrolyte in the circulating buffer tank 6 is led into an anode chamber 5, the concentration of the sodium chlorite is 1mol/L, and the flow rate is controlled at 100 mL/min. 0.5mol/L potassium sulfate electrolyte is continuously pumped into the cathode chamber 1 through a water pump 8, and the flow rate is 100 ml/min. Air was continuously pumped into the bottom of the anode chamber and the gas flow rate was controlled at 5 m/s. Then, a constant current of 1A was applied between the cathode 2 and the anode 4 and electrolysis was continued for 5 hours, and the concentration of chlorine dioxide in the anolyte was measured to calculate the selectivity of chlorine dioxide, which is shown in fig. 4.
As can be seen from fig. 4, the faradaic efficiency of the selective oxidation of chlorite to chlorine dioxide was close to 100% with a constant current of 1A for 5 hours, and almost no other chlorine-containing species were detected except for the chlorine dioxide product. The chlorine dioxide generating device of the invention has higher selectivity of generating the chlorine dioxide sterilizing agent.
Example 2:
capacity of the chlorine dioxide generating device for continuously generating high-purity chlorine dioxide: the chlorine dioxide generator assembled in example 1 was used to control the concentration of sodium chlorite in the anolyte to be 1mol/L and the flow rate to be 100 mL/min. Air was continuously pumped into the bottom of the anode chamber, and the gas flow rate was controlled at 5 m/s. The concentration of potassium sulfate in the catholyte is controlled to be 0.5mol/L, and the flow rate is controlled to be 100 ml/min. A constant current of 1A was applied between the cathode 2 and the anode 4, electrolysis was continued for 50 hours at a constant current of 1A, and the concentration of chlorine dioxide at the gas outlet of the anode chamber and the voltage change during electrolysis were detected, and the chlorine dioxide concentration and the voltage change during continuous electrolysis were shown in FIG. 5.
As can be seen from FIG. 5, the concentration of chlorine dioxide was maintained at about 6g/h and the voltage was maintained at about 2.2V during the 50-hour electrolysis. The sodium chlorite concentration detection and flow control instrument 7 can ensure that the device automatically feeds materials once every 10 hours, and the concentration of sodium chlorite in the circulating buffer tank is maintained at about 1mol/L, thereby ensuring the high-efficiency and high-selectivity conversion of chlorine dioxide. The chlorine dioxide generating device can continuously generate high-concentration chlorine dioxide sterilizing agent.
Example 3:
and (3) testing the automatic cleaning function of the device: the chlorine dioxide generator assembled in example 1 was used to control the concentration of sodium chlorite in the anolyte to be 1mol/L and the flow rate to be 100 mL/min. Air was continuously pumped into the bottom of the anode chamber and the gas flow rate was controlled at 5 m/s. The concentration of potassium sulfate in the catholyte is controlled to be 0.5mol/L, and the flow rate is controlled to be 100 ml/min. A constant current of 1A was applied between the cathode 2 and the anode 4, and electrolysis was continued for 1 week.
As can be seen from fig. 6, the concentration of chlorine dioxide generated by the apparatus slightly decreased after 4 days of continuous electrolysis, which is caused by the surface contamination of the monatomic integrated electrode. According to the program set by the sodium chlorite concentration detection and flow control instrument 7, the device is switched to a cleaning mode on day 5, deionized water in the cleaning solution storage tank 10 enters the circulating buffer tank 6 and then enters the anode chamber to clean the surface of the anode, and after 5 minutes of cleaning, the device is switched to a feeding mode again to continuously generate chlorine dioxide. The chlorine dioxide concentration produced by the device then returned to 6 g/h. The chlorine dioxide generating device can realize the automatic cleaning function and ensure that the device continuously generates the high-concentration chlorine dioxide sterilizing agent.
Example 4:
the application of the chlorine dioxide generating device in the aspect of air purification: and (3) placing the chlorine dioxide generator in a closed space with the formaldehyde concentration of 100ppm in the air, continuously working for 10 hours, and continuously monitoring the concentration change of the formaldehyde in the closed space. The formaldehyde concentration is plotted against time in FIG. 7.
As can be seen from fig. 7, the concentration of formaldehyde in the air in the enclosed space continuously decreased during the continuous operation of the chlorine dioxide generator, and formaldehyde was completely removed within 5 hours. The chlorine dioxide generating device can be applied to the aspect of air purification.
Example 5:
the application of the chlorine dioxide generating device in air disinfection: respectively culturing spore bacteria on nutrient agar culture medium flat plates in two biological safety cabinets with or without a connected chlorine dioxide generating device, starting the chlorine dioxide generating device, exposing the spore bacteria in the biological safety cabinets connected with the chlorine dioxide generating device to an atmosphere containing chlorine dioxide, closing the chlorine dioxide generating device after 30min, continuously culturing for 5h, and observing the average colony number of live spore bacteria on the two culture media after dyeing. The average number of spores on both media plates is shown in FIG. 8.
FIG. 8 shows the results in the connection twoIn the safety cabinet of the chlorine oxide generating device, live bacillus can not be observed on the culture medium flat plate exposed in the chlorine dioxide atmosphere, and the average colony number of the bacillus on the culture medium flat plate in the safety cabinet which is not connected with the chlorine dioxide device is as high as 4500cfu/m 3 . The chlorine dioxide generating device has obvious effect of killing bacteria and can be applied to the air disinfection.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The chlorine dioxide gas generating device based on the foamed titanium monatomic integral electrode is characterized by comprising an electrochemical reactor and a circulating feeding and cleaning device, wherein the electrochemical reactor comprises a cathode chamber (1), a cathode (2), a proton exchange membrane (3), an anode (4) and an anode chamber (5), the proton exchange membrane (3) is arranged between the anode (4) and the cathode (2), the cathode chamber (1), the cathode (2), the proton exchange membrane (3), the anode (4) and the anode chamber (5) are arranged and clamped,
the cathode (2) and the anode (4) are respectively connected with the negative electrode and the positive electrode of a power supply through leads;
the circular feeding and cleaning device comprises a circular buffer tank (6), a sodium chlorite concentration detection and flow control instrument (7), a raw material storage tank (9), a cleaning solution storage tank (10) and conveying equipment (8);
the circulating buffer tank (6) is connected with the anode chamber (5) through a pipeline, and the electrolyte containing sodium chlorite is recycled; the circulating buffer tank (6) is connected with the raw material storage tank (9) and the cleaning liquid storage tank (10) through pipelines, and the cleaning mode and the feeding mode are automatically switched through the sodium chlorite concentration detection and flow control instrument (7);
the anode (4) is a foamed titanium single-atom integral electrode, and the cathode (2) is a porous foamed nickel electrode.
2. The apparatus according to claim 1, wherein the titanium foam monatomic bulk electrode is based on titanium foam, and the transition metal monatomic or nanocluster active material is formed on the surface of the titanium foam.
3. A titanium foam monatomic monolith electrode-based chlorine dioxide gas generator as set forth in claim 2, wherein the transition metal monatomic is at least one of manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold for the titanium foam monatomic monolith electrode.
4. A titanium foam monatomic bulk electrode-based chlorine dioxide gas generator as claimed in claim 2, wherein the transition metal monatomic mass loading on the titanium foam monatomic bulk electrode is in the range of 0.01% to 20%.
5. A titanium foam monatomic bulk electrode-based chlorine dioxide gas generator as defined in claim 2, wherein the titanium foam monatomic bulk electrode has a porous structure, and the pore size of the micropores is in the range of 50 to 100 microns.
6. A titanium foam monatomic bulk electrode-based chlorine dioxide gas generator according to claim 1, wherein the anolyte is a sodium chlorite electrolyte; the cathode electrolyte is sodium sulfate or potassium sulfate solution; the cleaning solution is deionized water.
7. A titanium foam monatomic integrated electrode-based chlorine dioxide gas generator as claimed in claim 6, wherein the anolyte or catholyte concentration ranges from 0.1mol/L to 5 mol/L.
8. The application method of the titanium foam monatomic integrated electrode-based chlorine dioxide gas generation device based on any one of claims 1 to 7, wherein the titanium foam monatomic integrated electrode-based chlorine dioxide gas generation device is used for continuously producing high-purity chlorine dioxide gas, and comprises the following steps:
introducing electrolyte containing sodium chlorite into an anode chamber, introducing air into the anode chamber, introducing potassium sulfate or sodium sulfate electrolyte into a cathode chamber, introducing the electrolyte containing sodium chlorite from the bottom of the anode at a certain flow rate, flowing through the anode, and finally discharging from the upper end of the anode chamber; in the process, a voltage is applied between the cathode and the anode, sodium chlorite in the electrolyte is selectively converted into chlorine dioxide on the surface of the anode, and then the generated chlorine dioxide flows out along with air pumped in from the bottom of the anode.
9. The method of claim 8, wherein a constant voltage of 0.5V to 36V or a constant current of 0.1 to 50A is applied between the anode and the cathode, and a gas flow rate is controlled to be in a range of 0.001m/s to 10m/s and an electrolyte flow rate is controlled to be in a range of 1mL/min to 500 mL/min.
10. The application method of claim 8, wherein during the continuous electrolysis, the sodium chlorite concentration is detected in real time by a sodium chlorite concentration detection and flow control instrument, and the electrode surface cleaning and anolyte replenishing modes are switched as required.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5932085A (en) * | 1993-05-12 | 1999-08-03 | Sterling Pulp Chemicals, Ltd. | Chlorine dioxide generation for water treatment |
| TWM322947U (en) * | 2007-02-07 | 2007-12-01 | Jen-You Jang | High efficient manufacturing device of chlorine dioxide by electrolyzing |
| CN205774813U (en) * | 2016-06-16 | 2016-12-07 | 广州恒河环保设计研究院股份有限公司 | Sanitizer generating apparatus |
| CN207418874U (en) * | 2017-05-04 | 2018-05-29 | 优尼克生技股份有限公司 | Aqueous solution of chlorine dioxide production equipment |
| CN108570689A (en) * | 2018-04-24 | 2018-09-25 | 大连交通大学 | Electrolysis prepares the device and method of chlorine dioxide |
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2022
- 2022-05-11 CN CN202210537098.9A patent/CN115094462A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5932085A (en) * | 1993-05-12 | 1999-08-03 | Sterling Pulp Chemicals, Ltd. | Chlorine dioxide generation for water treatment |
| TWM322947U (en) * | 2007-02-07 | 2007-12-01 | Jen-You Jang | High efficient manufacturing device of chlorine dioxide by electrolyzing |
| CN205774813U (en) * | 2016-06-16 | 2016-12-07 | 广州恒河环保设计研究院股份有限公司 | Sanitizer generating apparatus |
| CN207418874U (en) * | 2017-05-04 | 2018-05-29 | 优尼克生技股份有限公司 | Aqueous solution of chlorine dioxide production equipment |
| CN108570689A (en) * | 2018-04-24 | 2018-09-25 | 大连交通大学 | Electrolysis prepares the device and method of chlorine dioxide |
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