CN1287010C - Ozone producing electrolyzer - Google Patents
Ozone producing electrolyzer Download PDFInfo
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- CN1287010C CN1287010C CN 02102900 CN02102900A CN1287010C CN 1287010 C CN1287010 C CN 1287010C CN 02102900 CN02102900 CN 02102900 CN 02102900 A CN02102900 A CN 02102900A CN 1287010 C CN1287010 C CN 1287010C
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- ozone
- battery
- electrolyzer
- ozone producing
- producing electrolyzer
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 103
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000011780 sodium chloride Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- -1 NaCl Chemical class 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 27
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- 239000008151 electrolyte solution Substances 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 claims description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims description 3
- 229910052987 metal hydride Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 34
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 10
- 230000001954 sterilising effect Effects 0.000 abstract description 8
- UUWCBFKLGFQDME-UHFFFAOYSA-N platinum titanium Chemical compound [Ti].[Pt] UUWCBFKLGFQDME-UHFFFAOYSA-N 0.000 abstract description 5
- 241000251468 Actinopterygii Species 0.000 abstract description 3
- 235000013399 edible fruits Nutrition 0.000 abstract description 3
- 235000019688 fish Nutrition 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 abstract description 2
- 235000013372 meat Nutrition 0.000 abstract description 2
- 238000002955 isolation Methods 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 229910006654 β-PbO2 Inorganic materials 0.000 abstract 1
- 230000008569 process Effects 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000005868 electrolysis reaction Methods 0.000 description 13
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000007600 charging Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 244000005700 microbiome Species 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010349 cathodic reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 230000003534 oscillatory effect Effects 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 2
- KRQUFUKTQHISJB-YYADALCUSA-N 2-[(E)-N-[2-(4-chlorophenoxy)propoxy]-C-propylcarbonimidoyl]-3-hydroxy-5-(thian-3-yl)cyclohex-2-en-1-one Chemical compound CCC\C(=N/OCC(C)OC1=CC=C(Cl)C=C1)C1=C(O)CC(CC1=O)C1CCCSC1 KRQUFUKTQHISJB-YYADALCUSA-N 0.000 description 1
- 241000224489 Amoeba Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000305071 Enterobacterales Species 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000702670 Rotavirus Species 0.000 description 1
- 241000607142 Salmonella Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000607626 Vibrio cholerae Species 0.000 description 1
- 208000034817 Waterborne disease Diseases 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 208000031513 cyst Diseases 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002458 infectious effect Effects 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000013547 stew Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 1
- 229940006158 triiodide ion Drugs 0.000 description 1
- 229940118696 vibrio cholerae Drugs 0.000 description 1
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The present invention relates to an electrolytic tank for generating ozone, which is manufactured by that a platinum titanium mesh is used as a cathode, a platinum titanium mesh plated with beta-PbO2 is used as an anode, and a battery and a super-high capacitor are used as DC power supply. The isolation of a thin film between the cathode and the anode is not needed, and neutral salt, such as NaCl, can be used to promote the generation of ozone. The electrolytic device comprising a container, two electrodes and a bubble generator can be directly put in water needing ozone treatment. Because the battery can provide electric power for the generation of ozone, the device can be used for places needing ozone treatment, and a mains supply is not needed. The electrolytic device can be used for pharmaceutical industry, the water sterilization of families, the surface cleanness of semiconductors, meat, fish, fruit, etc., and the sterilization of water for SPA and personal hygiene.
Description
Technical field
The invention relates to a kind of with ozone generating apparatus, and particularly relevant for a kind of with the ozoniferous electrolyzer of electrolytic process.
Background technology
In all dirts of water, comprise abiogenous etiologies such as enterobacteria, germ and former cysts, it is acute ill or even dead that the people who drinks polluted water is produced.Under comparing, other pernicious effect as the pollution of heavy metal is non-infectious often, and slowly outbreak.According to sanitation degree, the caused water-related disease of pathogenic organisms body such as intestinal bacteria, salmonella, vibrio cholerae, rotavirus and amoeba histolytica is easier to outburst and causes the popular state of an illness.The sterilization and disinfection technology that is usually used in eliminating or filter the biological pollutant in the water supply has 4 kinds, i.e. chlorineization, ozonize, hyperfiltration and ultraviolet ray.In water, effective 150 times of ozone, fast 3000 times of the speed ratio chlorine of its kill microorganisms cell than chlorine.The more important thing is that ozone left resistates after disassembling cytolemma is an oxygen.Ozone is to the destruction of microorganism, only passes genetic stew than ultraviolet ray and hinders it and grow up much effective again.In addition, hyperfiltration costs an arm and a leg on the one hand, can only stop that on the other hand microorganism but do not eliminate pathogeny.Therefore, in fact ozone has become the main sterilant of some city tap-water supplies in the world.
Ozone is the allotropic substance of oxygen, is the single molecule that three Sauerstoffatoms are formed.At occurring in nature, lightning can split into oxygen molecule single atom, and Sauerstoffatom is combined into the trilateral molecule of short lifetime again with oxygen molecule.Ozone also can continue to generate because of the ultraviolet radiation of the sun in the atmospheric layer outside.But, ozone also can be artificial, and it is that thousands of volts of voltages are applied on several aluminized Glass tubings, the air between pipe can be changed into pungent gas.Existing many reports that utilize preceding method (or be called " glow discharge ") on the document, United States Patent (USP) for example: the 5th, 503, No. 808, the 5th, 523, No. 310, the 5th, 824, No. 274, the 6th, 134, No. 806 just wherein several pieces of writing such as grade also have many ozone generation device commodity that utilize silent discharge simultaneously on the market.Producing ozone with glow discharge not only needs high-voltage, also need use dry air or pure oxygen.Because oxygen is to be decomposed at high voltage electric field, nitrogen also can be decomposed simultaneously, and produces NO
XAnd so on dangerous pollutant.The aqueous vapor of removing in the air inlet of discharge ozone producer is in order to prevent HNO
3With HNO
2Generation, these acid have corrodibility to producer.Reducing the used airborne aqueous vapor of ozone generation is not the part minor matter, but can reduce the dew point (dew point) of air.The reduction of dew point can significantly improve the generation of ozone, and for example dew point is when-40 ℃ are reduced to-50 ℃, and the generation efficient of ozone improves 15%.Yet humidity control is not the unique difficulty that generates ozone with glow discharge, and other problem still has ozone to leak (all harmful to operator and environment), the solubleness of ozone in water, and electrical safety all must think better of.Therefore, develop the ozone generation method of another high-level efficiency and less restriction, will help the universalness of ozone sterilization method.
Having come out with the synthetic ozone of electrolytic process, (a first piece of writing is reported as: Schonbein more than 160 years; Ann., Vol.50, P.616 (1840)), applying for a patent also of such technology surpasses 30 years (for example, United States Patent (USP): 3,256, No. 164, on June 14th, 1966).During electrolysis, be on the anode of electrolyzer, to apply low dc voltage and high current density, to produce ozone.Though electrolysis process consumes more energy (about 6: 1) than glow discharge, electrolytic process has higher current efficiency (electrolytic process can surpass 50%, and electric discharge is about 2%), therefore can remedy the loss of energy.Also have, produce ozone with electrolytic process and there is no such as humidity control, ozone leaks, NO
XByproduct is with ozone solution degree problems such as (ozone must water-solublely just produce the processing effect).The parameter that influences of the ozoniferous output of electrolytic process has: anode material, electrolytic solution, voltage, current density and solution temperature.Report as Foller and Tobias discloses: " The AnodicEvolution of Ozone "; J.Electrochem.Soc., Vol.129, No.3, March 1982; PP 506-515 (this report and in the present invention as a reference) is higher than 50% ozone current efficiency at 0 ℃ 7.3M HPF
6In the aqueous solution, apply 0.5A/cm
2Electric current is in β-PbO
2Anode and obtaining.Basically, it is similar to brine electrolysis that electrolysis produces ozone, and just the generation of ozone system uses as β-PbO
2Have high oxygen overpotential material as anode.But, oxygen can produce on anode still that (ozone current efficiency promptly is O
3Concentration and O
2The ratio of concentration), hydrogen then produces on negative electrode.Manyly promptly settle an ion-exchange membrane, produce in electrolyzer with oxygen and mix, as to be disclosed in the patent No. be 4 to prevent hydrogen at two interpolars with the ozoniferous research of electrolytic process, 416,747,4,935,110,5,114,549,5,927,196,5,997,702 and 6, in 143,163 the United States Patent (USP), these patents also all and in the present invention as a reference.At report of the Article of Foller and U.S. Patent number: in 4,316,782,4,541,989 and 5,154,895 (these three pieces of patents and as a reference), all use a fluorine-containing negatively charged ion as ionogen, with the output of raising ozone in the present invention.Yet fluo anion generally has corrodibility, may not be suitable for general purpose ozone generation device.Carry out with low dc voltage and big electric current because electrolytic process produces ozone, so DC electric power provides just and conforms to the characteristic of ultra-high capacity device, so the present invention uses the capable ozone generation of electric power module that comprises battery and ultra-high capacity device.In addition, the present invention is also with NaCl, KCl, NaNO
3Or KNO
3Etc. neutral salt replacement fluorine thing as ionogen, and normal temperature and without the film isolated electrode under carry out electrolysis.Salt is immanent commodity, though when water temperature was high, the current efficiency of ozone can be hanged down, normal temperature is kept easily more than low temperature.Therefore, can make one simple, par according to the present invention, and wieldy ozone generation device, can be used for the surface sterilization of the sterilization, fish, fruit etc. of the water at industry, family and SPA center, and available manufacturing collutory ozoniferous is to keep oneself clean.
Ozone is a kind of strong but oxygenant of environmental protection.It can kill morbific microorganism and decompose many organic compound, and these pollutents are difficult to remove in water usually.Ozone is after finishing disinfection, and it only produces O
2By product, another benefit that can obtain making water oxygen level to increase again.With ozonize water may be to make the most effective of nontoxic water and technology fast.Yet the carrying out of ozonize should be safety and economy.
Summary of the invention
One object of the present invention is to be provided in direct ozoniferous electrolytic process in the water, with the ozone problem not soluble in water of avoiding electric glow discharge method to be met with.
Another object of the present invention is promptly forming power module with battery and ultra-high capacity device, to provide ozone generation required energy.
For achieving the above object, the invention provides a kind of ozone producing electrolyzer, comprising: two mesh electrodes, it is immersed in the electrolytic solution, and this two mesh electrode is with a direct current power supply continous way or the power supply of intermittent type ground; One bubble generator is configured in this electrolyzer, and this bubble generator is in order to provide bubble to this electrolytic solution; Wherein comprise at least a neutral salt in this electrolytic solution; One of this two mesh electrode is an anode; And another mesh electrode is a negative electrode.
For making electrode have stability and economy, the present invention uses platinum titanium mesh to be negative electrode, and to be coated with β-PbO
2Platinum titanium mesh be anode.Compare with glassiness carbon material with other anode material such as platinum, anode of the present invention is cheap, but its function is not relatively poor.Moreover electrolyzer of the present invention need not be isolated anode and negative electrode with film, and with the generation that improves ozone as neutral salts such as NaCl.The electrolyzer that contains an electrode and a bubble generator of the present invention can directly place and need disinfectant water, therefore electrode is installed on the water pipe, can become continuously, flows through the ozonize device of formula.
Low voltage is preferably supplied with the ultra-high capacity device with the pulse electric power of big electric current, and it is the energy storage component of rapid charge of a kind of energy and discharge.Contain an oscillatory circuit in the module, the electric power that puts on electrode can be controlled via the recurrence interval that changes circuit.Once all can be used for the charging of ultra-high capacity device with secondary cell, electrical condenser is supplied and is produced the required immediate current of ozone.Use of the present invention is not only convenient, and does not have electrical hazard, because it is with low voltage operating.
Description of drawings
Fig. 1 is according to a preferred embodiment of the present invention, and mesh electrode is assembled in the electrolyzer with parallel, to produce ozone;
Fig. 2 is that mesh electrode places electrolyzer in the concentric(al) circles mode according to another preferred embodiment of the present invention, to produce ozone;
Fig. 3 is according to preferred embodiment of the present invention, comprises battery, ultra-high capacity device, and the circuit structure of the power module of oscillatory circuit dress, produces ozone with supply pulsed electrical power;
Fig. 4 A is according to preferred embodiment of the present invention, ozone generation amount and the relation curve that applies voltage;
Fig. 4 B is according to preferred embodiment of the present invention, the relation curve of ozone generation amount and impulse ratio.
101,202: electrolyzer 103,200: electrolytic solution
105,204: meshed anode 107,206: mesh cathode
109,208: bubble generator 301: battery
302,309,310: diode 303: the ultra-high capacity device
304,307,312: resistor 305,306:C-MOS NOT lock
308: variohm
311: electrical condenser
313:N passage FET
314: load
1,2; Electrode
Embodiment
As everyone knows, when water during by electrolysis, H
2To on negative electrode, produce, and O
2On anode, produce, describe as following half-reaction formula:
Cathodic reaction
(1)
Anodic reaction
(2)
The anodic reaction that is produced as a high potential of ozone shown in half-reaction formula (3)
For improving the current efficiency of ozone generation, i.e. O
3Concentration is to O
2The ratio of concentration, anode must use the material with high oxygen overvoltage.Platinum and glassiness carbon material promptly are the effective and stable candidate materials of ozone generation.Above-mentioned precious metal and the selling at exorbitant prices of glassiness carbon material can't be in order to make large-scale ozonizer.But, plumbous oxide, particularly β-PbO
2Be the more cheap desirable anode surrogate of more preceding two materials.Because Pb is in its highest state of oxidation, so PbO
2Under strong anodic polarization, can stablize.β-PbO
2Be to be deposited on the suitable substrates with oxidation style, for example platinum titanium mesh (representing) with Ti/Pt, be coated with the titanium net of iridium oxide, or be coated with the titanium net of tindioxide, and use the aqueous solution that contains lead nitrate, nitric acid and Sodium Fluoride to be electroplate liquid.That knows this technology knows β-PbO per capita
2Electrochemical deposition method, so locate to repeat no more.Based on stability (promptly resisting the ability of high oxidation state) and cost, the present invention selects Ti/Pt as the anodic base material, is negative electrode with the Ti/Pt that does not reprocess.Fig. 1 is the electrode arranged parallel of a preferred embodiment of the present invention, label 105 be meshed anode (Ti/Pt/ β-PbO
2), 107 is mesh cathode (Ti/Pt), it places the electrolyzer of label 101.Air enters in the electrolytic solution 103 via bubble generator 109, and this liquid can be made into being dissolved in as 10gNaCl in 1 liter of deionized water (deionized water, DI water), to suppress H in the half-reaction formula (1)
2Generation.Air has two tasks at this, and the one, take the ozone that in solution, produces out of, another is for providing the required raw material of cathodic reaction represented as half-reaction formula (4), and this reaction may surpass half-reaction (1), makes H
2Generation is suppressed.
Fig. 2 is another preferred embodiment, in electrolyzer 202, anode 204 and negative electrode 206 be concentric(al) circles and with anode placed in the middle between.Similarly, air flows to negative electrode 206 via bubble generator 208, carries out above-mentioned functions.Electrolytic solution 200 can be salt solution, or needs the water of ozonize.In other words, comprise electrolyzer 202, electrode 204 and 206, the electrolyzer that reaches bubble generator 208 can directly place water, as aquarium, to carry out ozonize when participating in the cintest, makes water keep clean state.Even water flows through electrode, enough ozone (for example, the city water processing establishment often uses 1-3ppm ozone) also can produce in electrolyzer, with sterilization drinking-water.So the electrolyzer carried of the present invention is installed on select location on the water pipe with electrode, can form successive and flow through the formula ozonation system, carries out online water treatment.As the electrolyzer that Fig. 1 and Fig. 2 drew, can be made into the spatial size of the utensil of packing into, in the handle as brush, be used for medical instrument and semi-conductive surface cleaning, and the surface sterilization of meat, fish and fruit.Ozone can be effectively and the processing of putting things right once and for all is provided in many dry types and wet type production application economically.
Traditionally, the ozone concn in the water is to measure with iodimetry.In this method, iodide ion I
-By ozone oxidation is iodine molecule I
2, iodine molecule forms the triiodide ion I of brown again with iodide ion
3 -, the reaction metering is as follows:
Electrolytic process is better than one of advantage of glow discharge in order to produce ozone, is that low dc voltage can be used for wet process as 3～18V.The voltage (often using thousands of volts) that this dc voltage is required far below the aura method, meaning is that the cost of electrolytic process is lower, and need not transformer, civil power, and the strick precaution of electrical hazard.Though at the O that produces equivalent
3, electrolytic process may need the electric current higher than glow discharge, and only the energy requirement of electrolytic process can satisfy with an exquisite design.That is exactly to supply required voltage and electric current economically and effectively with the ultra-high capacity device.The ultra-high capacity device can store the energy of battery no better than, and the ultra-high capacity device can discharge and recharge as traditional capacitor apace on the other hand.Therefore, the ultra-high capacity device is the desirable component in the ozoniferous DC power supply of electrolytic process." ultra-high capacity/battery " that Fig. 3 comprises I, II and three function squares of III blendes together the circuit layout of electric power.Square I is a power circuit, and wherein battery 301 is in parallel with ultra-high capacity device 303, and with diode 302 protection batteries 301; to prevent the reverse charge of ultra-high capacity device 303; this battery 301 for example is a drying battery, lead-acid cell, nickel-cadmium cell; nickel metal hydride battery; lithium ion battery, lithium macromolecule battery, fuel cell; metal-air battery, and solar cell.The energy that utilizes battery 301 to be provided, ultra-high capacity device 303 can produce O to load 314 or electrode 1 and 2 (wherein 1 is anodal, and 2 is negative pole) power supply then
3 Load 314 constitutes switching circuit square II with N passage FET 313.Along with FET313 does to switch rapidly with hundreds of hertz frequency, ultra-high capacity device 303 is promptly to load 314 supply pulse electric power.The operating frequency of FET313 and periodic system are by being controlled with the represented self-excited type multi-resonant oscillating circuit of square III.Vibrator is mainly by high speed C-MOS NOT lock, 305 and 306 compositions, these NOT locks are called phase inverter again, i.e. its output permanent with import opposite.For example, if input A is 0, then exporting B is 1, and output C is 0.When the B point is 1, a charging current is promptly arranged from B flow through resistor 307 and 311 chargings of 310 pairs of electrical condensers of diode.Similarly, same charging current resistor 304 to the A points of also can flowing through.In case electrical condenser 311 is charged to a setting voltage, the A point also becomes at 1 o'clock simultaneously, and B names a person for a particular job and immediately transfers 0 to, and the C point also will become 1.
In the moment that electrical condenser 311 stops to charge, electrical condenser promptly transfers discharge to, makes NOT lock 306 be output as rectangular wave, and the resistor 312 of flowing through switches FET 313.The same time that electrical condenser 311 begins to discharge, the A point becomes 0, makes the B point become 1 again, launches another time charge and discharge cycles of electrical condenser 311.In fact, NOT lock 305 and 306 functions with the capable flip-flop of self-excitation mode (flip-flop).The frequency of vibrator is mainly decided by the resistance of resistor 307 and the electrical capacity of electrical condenser 311.Yet resistor 304 and 308 also can influence oscillation frequency and cycle.Diode 309 and 310 constitutes a chopper.When variohm 308 is threaded to low order end, be maximum by B point to the charging current of electrical condenser 311, so electrical condenser 311 is with shortest time charging and discharge, and the output periodic width that this moment, C order is a minimum.Thus, " ON " time of FET 313 is minimum relatively, and load 314 is minimum from the electric power that the ultra-high capacity device obtained.On the other hand, when variohm 308 was threaded to high order end, the charging current of ordering from B was minimum, electrical condenser 311 discharges and recharges with the slowest speed, the output width maximum that this moment, C was ordered, so the ON time of FET 313 is maximum relatively, load 314 obtains maximum power.In sum, Fig. 3 is the power supply of a preferred embodiment, and the ozoniferous electric power size of its supply electrolysis can be selected 1% to 99% change by the impulse ratio of FET 313.Therefore, required ozone amount can produce with the electrolytic process of the impulse ratio that changes circuit.The embodiment of following example only is used for confirming effect of the present invention, and unrestricted its scope, it is a kind of simple that the present invention can provide, and electrolysis economic and that conveniently use produces ozonizer and prepares the fresh water of clarification.
Embodiment one
Use is according to the electrolyzer of Fig. 1, and different ozone amounts can be decided to produce under the voltage applying different DC.Electrolyzer adopts following condition:
Anode: Ti/Pt/ β-PbO
2Negative electrode: Ti/Pt
Electrode area: 10cm
2
Voltage: provide fixed voltage with a DC power supply unit
The 1wt.%NaCl aqueous solution of electrolytic solution: 100ml
Solution temperature: room temperature
Air velocity: 11/min
Electrolysis time: 1min
Ozone concn is measured with iodimetry.
Table 1 lists ozone concn and respectively applies under the voltage electric current that is write down.
| Apply voltage (V) | Record current (A) | O 3Output (mg) |
| 6 | 0.28 | 0.79 |
| 10 | 0.67 | 1.68 |
| 12 | 0.90 | 1.98 |
| 16 | 1.30 | 2.13 |
| 18 | 1.64 | 2.18 |
| 20 | 1.60 | 2.00 |
| 24 | 2.10 | 1.50 |
Ozone amount under the different dc voltages of table 1.
To applying the voltage mapping, promptly get Fig. 4 A with ozone amount.As seen from the figure, under above-mentioned electrolytic condition, the generation of ozone reaches maximum when 18V.
Embodiment two
Use electrolyzer and the electrolytic condition identical with embodiment one, different ozone concns can produce in different electrolytes under 24V decides voltage, and the result is as follows:
| Electrolytic solution | Electric current (A) | O 3Amount (mg) |
| 10wt.％NaCl | 3.12 | 2.79 |
| 30wt.％NaCl | 6.34 | 1.98 |
| 10wt.％KNO 3 | 1.98 | 0.04 |
| 10wt.％NaBF 4 | 0.54 | 0.03 |
Embodiment three
The electrolyzer identical with embodiment one removes electrolytic solution, and promptly 10wt.%NaCl passes through electrode with two kinds of different in flow rate.Ozone one produces and promptly is pulled away, and collects the effluent liquid of 100ml then.Ozone amount under each flow velocity is measured with iodimetry.
| Flow velocity (ml/min) | Electric current (A) | O 3Output (mg) |
| 30 | 0.98 | 2.57 |
| 100 | 0.74 | 1.67 |
The present invention's online ozonize of can be used for continous way is used for the sterilization of water obviously.
Embodiment four
The electrolyzer identical with embodiment one, remove the lead-acid cell of 12V and ultra-high capacity device as the power supply of Fig. 3 come electrolysis generation ozone.Table 2 lists the ozone amount under the different impulse ratios:
| Impulse ratio (%) | Ozone amount (mg) |
| 25 | 0.88 |
| 50 | 1.51 |
| 75 | 2.26 |
| 90 | 2.48 |
Table 2. ozone amount and impulse ratio
With the mapping of ozone amount paired pulses ratio, promptly get Fig. 4 B.According to expectation, the ozone output under the big impulse ratio of healing are higher, and this is because of more energy supply electrolysis is arranged.It will be easily that this kind is provided with the application that need not high ozone concentration.Therefore by the control of impulse ratio, promptly be easy to obtain the ozone amount of custom-made.The foregoing description points out that but the true electrolysis of the present invention produces ozone and does water treatment.
Claims (12)
1, a kind of ozone producing electrolyzer is characterized in that, this electrolyzer comprises:
Two mesh electrodes, it is immersed among the electrolytic solution, and this two mesh electrode is with a direct current power supply continous way or the power supply of intermittent type ground;
One bubble generator is configured in this electrolyzer, and this bubble generator is in order to provide bubble to this electrolytic solution; Wherein,
Comprise at least a neutral salt in this electrolytic solution;
One of this two mesh electrode is an anode; And
This another electrode of two mesh electrodes is a negative electrode.
2, ozone producing electrolyzer as claimed in claim 1 is characterized in that, is attached with one deck β-PbO on this anode
2
3, ozone producing electrolyzer as claimed in claim 1 is characterized in that, this anodic base material is that titanium metal plates a material, and this material is selected from one of group that is made up of platinum, iridium oxide and tindioxide.
4, ozone producing electrolyzer as claimed in claim 3 is characterized in that, more is coated with one deck β-PbO on this anode
2
5, ozone producing electrolyzer as claimed in claim 1 is characterized in that, this negative electrode is that titanium metal plates a material, and this material is selected from by platinum, one of group that iridium oxide and tindioxide are formed.
6, ozone producing electrolyzer as claimed in claim 1 is characterized in that, this neutrality salt is selected from by NaCl, KCl, NaNO
3, and KNO
3One of group that is formed.
7, ozone producing electrolyzer as claimed in claim 1 is characterized in that, this direct supply comprises a battery.
8, ozone producing electrolyzer as claimed in claim 7, it is characterized in that this battery is selected from the group that is made up of drying battery, lead-acid cell, nickel-cadmium cell, nickel metal hydride battery, lithium ion battery, lithium macromolecule battery, fuel cell, metal-air battery and solar cell.
9, ozone producing electrolyzer as claimed in claim 1 is characterized in that, this direct supply is made up of battery, ultra-high capacity device and vibrator.
10, ozone producing electrolyzer as claimed in claim 9 is characterized in that, this battery is selected from by drying battery, lead-acid cell, nickel-cadmium cell, nickel metal hydride battery, lithium ion battery, lithium macromolecule battery, fuel cell, metal-air battery reaches the group that solar cell is formed.
11, ozone producing electrolyzer as claimed in claim 9 is characterized in that, this vibrator comprises self-excited multivibrator.
12, a kind of control method of ozone producing electrolyzer is characterized in that, comprising:
Ozone producing electrolyzer as claimed in claim 1 is provided; And
Adjust the impulse ratio of the circuit of this direct supply, and the control ozone output.
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|---|---|---|---|
| CN 02102900 CN1287010C (en) | 2002-01-30 | 2002-01-30 | Ozone producing electrolyzer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02102900 CN1287010C (en) | 2002-01-30 | 2002-01-30 | Ozone producing electrolyzer |
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| CN1287010C true CN1287010C (en) | 2006-11-29 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101054679B (en) * | 2007-02-14 | 2010-05-26 | 浙江工业大学 | A kind of method for preparing ozone by low pressure electrolysis |
| CN104862732A (en) * | 2015-05-05 | 2015-08-26 | 大连理工大学 | Method and equipment for electrochemically generating ozone from oxygen-containing gas |
| CN105002517B (en) * | 2015-07-01 | 2018-06-26 | 苏州聪歌新能源科技有限公司 | The production technology and ozone generation device of a kind of ozone generation electrode and its anode |
| CN105063728A (en) * | 2015-08-18 | 2015-11-18 | 江苏金曼科技有限责任公司 | Anti-corrosive platinum-titanium mesh |
| CN105063659B (en) * | 2015-09-15 | 2018-05-08 | 苏州铂瑞电极工业有限公司 | A kind of electrolysis unit |
| WO2018048393A1 (en) | 2016-09-07 | 2018-03-15 | Colgate-Palmolive Company | Product container with electrochemistry device |
| JP7069611B2 (en) * | 2017-09-13 | 2022-05-18 | 株式会社豊田中央研究所 | Electrochemical cells and photosynthetic equipment |
| CN111206265B (en) * | 2018-11-21 | 2021-06-04 | 元智大学 | Gas-water circulation system and its multifunctional water electrolysis device |
| CN110668534A (en) * | 2019-11-07 | 2020-01-10 | 无锡迅朗联大机能水技术研究院有限公司 | Formula of electrolyte solution for non-diaphragm acidic electrolyzed water generator |
| CN113925431B (en) * | 2021-11-12 | 2024-03-12 | 珠海格力电器股份有限公司 | Sterilizing water generating device and dish washer |
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