CN101360848A - Ozone generating electrolysis cell - Google Patents
Ozone generating electrolysis cell Download PDFInfo
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- CN101360848A CN101360848A CNA2006800516790A CN200680051679A CN101360848A CN 101360848 A CN101360848 A CN 101360848A CN A2006800516790 A CNA2006800516790 A CN A2006800516790A CN 200680051679 A CN200680051679 A CN 200680051679A CN 101360848 A CN101360848 A CN 101360848A
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 29
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 39
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 39
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000000084 colloidal system Substances 0.000 claims abstract description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000007784 solid electrolyte Substances 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 abstract description 17
- 230000006835 compression Effects 0.000 abstract 1
- 238000007906 compression Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 239000008246 gaseous mixture Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000009824 pressure lamination Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/13—Ozone
-
- 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
-
- 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
Abstract
The ozone generating electrolysis cell (10) according to the invention has a negative electrode (13) and an ozone generating positive electrode (16) comprising a mixture of lead dioxide and polytetrafluoroethylene (PTFE). A proton conducting solid electrolytic membrane (15) is arranged between the negative and positive electrodes (13, 16). The ozone generating electrolysis cell (10) also comprises an electrically conducting, liquid and gas permeable first electrode support (17) in contact with a side of the positive electrode (16) located opposite to the membrane (15), wherein said side of the electrode support (17) has a surface covered with a platinum-containing layer. The positive electrode (16) is made of a mixture prepared by the high-pressure compression of lead dioxide grains of colloid size and PTFE filaments having a dimension of at most 1 mm. Furthermore, the negative electrode (13) is adjoined to a side of the membrane (15) located opposite to the positive electrode (16) by a given compressing force and is formed on a surface of a porous second electrode support (12).
Description
Technical field
The present invention relates to a kind of ozone generating electrolysis cell, it ozone generation positive electrode, one that comprises that a negative potential, comprises the mixture of lead (IV) oxide compound (being called plumbic oxide) and polytetrafluoroethylene (PTFE) is arranged on film between negative potential and the positive electrode and first electrode support of the permeable conduction of liquids and gases, one side contacts of this first electrode support and positive electrode, be positioned to relatively with described film, the described side of electrode support has one and is coated with the surface that contains platinum layer.
Background technology
The known multiple commercial run that utilizes electrolyzer to come to make ozone from water.In these processes, use has the electrolyzer that is used to realize electrolysis and therefore is used for ozoniferous middle body, and the negative electrode (negative potential) and that described middle body comprises an anode (positive electrode) that has the smooth plate form usually, have a same configuration is arranged on proton exchange membrane between anode and the negative electrode (Nafion for example
TM), this proton exchange membrane is made up of the solid electrolyte with smooth plate form, as at for example U.S. patent No.6, described in 328,862.
According to cited paper, anode itself is the porous member that is made of titanium usually and has the ability that can see through liquids and gases.On (interior) surface of proton exchange membrane, be applied with a thin platinum layer by an electroplating process at anodic usually.Between this platinum layer and proton exchange membrane, be provided with an electrode layer, described electrode layer comprises metal or semimetallic conductor and/or its oxide compound (for example plumbic oxide), it is characterized in that the superpotential of high evolution or deposition potential with respect to oxygen.Near the anodic outside surface, promptly be provided with an anode side collecting board (being also referred to as electrode support) that contacts with anode with proton exchange membrane facing surfaces place at it, it provides the electrical connection between anode and the power supply on the one hand, and the outlet that is used for oxygen/ozone gas of being produced is provided on the other hand.In addition, the anode side collecting board also can make the required water of electrolysis can be directed to anode side itself.
Negative electrode also comprises one by porous material or wherein have the material of suitable passage and---be generally stainless steel or titanium and also have the ability that can see through liquids and gases---member of making.On (interior) surface of proton exchange membrane, be applied with metallic electrode layer at negative electrode to be used to produce hydrogen.The platinum layer that this metallic electrode layer is normally thin.Outside surface near negative electrode, be provided with a cathode side collecting board (being also referred to as electrode support) that contacts with negative electrode, described cathode side collecting board provides being electrically connected between negative electrode and the power supply on the one hand, on the other hand electrolysis is required water guiding proton exchange membrane and by this proton exchange membrane guiding anode and be provided for the outlet of the hydrogen that produced where necessary.
Above-mentioned multi-layer electrode structure is contained in the electrolyzer chamber that suitably forms.For making easy installation, the electrolyzer chamber is formed by two halfbodies usually, and they are aligned and are fixed together by means of for example tie-bolt in the mode that seals.Be used for the required pressure of intact contact between the adjacent electrode structure floor also the screwing fixedly each other of two halfbodies by the electrolyzer chamber provide.
In the working process of ozone generating electrolysis cell with said structure, water is infeeded the cathode side of electrolyzer, and arrives proton exchange membrane and arrive anode by proton exchange membrane via porous cathode side collecting board and porous cathode side self (or be formed on wherein passage).When applying the voltage that is used for electrolyzer simultaneously, the electrolysis of water begins, and positively charged hydrogen ion moves to negative electrode from anode by proton exchange membrane.Simultaneously, produce oxygen and ozone owing to electrolysis and at the anode place.Ozone transformation efficiency coefficient, promptly therefore the amount of the ozone in the oxygen that produces, can influence the ozone generation ability of electrolyzer by the suitable manufacturing technology of anode electrode layer significantly by the quality and the working parameter decision of anode electrode layer.
According to a kind of common manufacturing processed of the electrode layer that comprises plumbic oxide, the plumbic oxide film is formed on the anode by plating.Very unfairness of the electrode layer that obtains thus/inhomogeneous this means the variation of the surface conductivity/specific conductivity (resistance) of electrode layer.In addition, the electrode layer of making by plating may be difficult to form, and it is very firm and break easily, therefore is not suitable for being used to comprising the batch process of the ozone generating electrolysis cell of solid electrolyte.
Have in the replacement method of the electrode layer that comprises plumbic oxide of independent plate form in manufacturing, the micropore of thin porous PTFE plate is filled the mixtures of material with plumbic oxide and proton exchange membrane, as at Japanese Patent No.3,504,021 and U.S. patent No.6, described in 054,230.Proton exchange membrane is placed on the member that obtains thus, and then, it is surface-coated to contain platinum material.Subsequently, this multilayered structure being placed temperature is under 120 ℃-140 ℃ the hot pressing.Repressed pressure lamination member is inserted between anode and the negative electrode, and is accommodated in then in the electrolyzer housing to obtain electrolyzer.The shortcoming of the maximum of this method is that plumbic oxide is a kind of very unstable compounds, easily owing to heat is decomposed.Therefore, when in higher following time of temperature, because the decomposition of plumbic oxide, form the zone with different electroconductibility gradually in some part of the anode electrode laminar surface of making by hot pressing, the operation with electrolyzer of kind electrode layer becomes unstable.
U.S. patent No.6,328,862 disclose a kind of method that is used to make the anode electrode layer that comprises plumbic oxide, wherein, disperse thing, lead dioxide powder and volatility dispersion agent (being preferably ethanol or Virahol) to mix PTFE, and the mixture that preferably will obtain thus by calendering be configured as one as thin as a wafer plate and for example dispersion agent is evaporated by heating.Each step of making electrode layer is all carried out being to the maximum under 100 ℃ the temperature, to avoid the possible thermolysis of plumbic oxide.The PTFE content of the mixture that obtains by this method is about 5% by weight, and film self is inflexible, break easily and have less ductility.In addition, cost as this electrolyzer of ozone generating electrodes/electrode layer---wherein, electrolyzer comprises plumbic oxide/PTFE film of being made by the liquid phase starting material---is because the use of corresponding solvent and dispersion agent and owing to increasing in its processing of carrying out after described layer evaporates.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of ozone generating electrolysis cell, make it possible to solid-phase raw materials, use dispersion agent to make the ozone generating electrodes at ambient temperature and not.Another object of the present invention is to provide the mixing material of a kind of plumbic oxide and PTFE, for example to be used for the anode of ozone generating electrolysis cell, described mixing material is because its PTFE content is higher relatively but have elasticity and ductile, can prepare at ambient temperature and available less technological step and to produce such as the present cost that plumbic oxide/the PTFE film is lower commonly used.Another purpose of the present invention is to provide a kind of negative electrode side (cathode side) electrode structure, and this electrode structure also has the permeable ability of liquids and gases owing to its structure inherently except its electroconductibility and physical strength.
Described and other purpose of the present invention realizes by a kind of ozone generating electrolysis cell is provided, wherein, positive electrode (being anode) is made by a kind of mixture, and described mixture has the plumbic oxide particulate of colloid size by high-pressure molding and PTFE silk that size is 1mm to the maximum is prepared; Negative potential (being negative electrode) to a side of described film, is positioned to relatively with positive electrode by given engage pressure, and is formed on the surface of a porous second electrode support.
Preferred other embodiment according to ozone generating electrolysis cell of the present invention is described by dependent claims 2-10.
Description of drawings
Describe the present invention below with reference to the accompanying drawings in detail, wherein:
Figure 1A is the sectional view that is used for according to a preferred embodiment of the electrode structure of ozone generating electrolysis cell of the present invention;
Figure 1B is the synoptic diagram of amplification of material structure of a preferred embodiment of second electrode support that is used to support the negative potential of a part that forms the electrode structure shown in Figure 1A; And
Fig. 2 is the longitudinal section of the ozone generating electrolysis cell that assembles, comprising the electrode structure that briefly shows in Figure 1A.
Embodiment
Being used in electrode structure 10 according to the Figure 1A in the ozone generating electrolysis cell of the present invention mainly comprises negative potential (or negative electrode) 13, ozone generation positive electrode (or anode) 16, is arranged on proton exchange membrane 15 between the described electrode 13,16 and first (positive electrode or anode side) electrode support 17 of a side relative with described film 15 that is arranged on positive electrode 16.Described electrode support 17 is arranged on one (anode side) supporting member 18, and this supporting member is provided with the through hole 19 that is used to electrically contact.Electrode 13 is formed on second (cathode side) electrode support 12, and this electrode support 12 is arranged on (cathode side) supporting member 11.
Cathode side supporting member 11 is made by plastic material special, that have chemoresistance, and it is shaped as a for example annular element.But supporting member 11 can be made by any other material, also can have any other shape obviously.
One essential condition of electrolyzer valid function is the good electrical contact between electrode 13,16 and the film 15.Therefore, electrode 13 forming on the electrode support of being made by the titanium frit 12 has crucial importance.In electrode structure 10 according to the present invention, it is preferred using the platinum powder (so-called platinum black) of very thin for negative potential 13.
Do not using shielding gas (that is, under the ambient air) under envrionment temperature and the pressure and platinum black is being applied on the electrode support 12 with the form of suspended substance.Described suspended substance is that the aqueous solution of the sodium laurylsulfonate (SDS) of 0.001mol/l is made by 40mg platinum black and 1ml concentration.For making the suspended substance homogenizing, used ultrasonic bath 5 minutes.Suspended substance keeps stable and that is to say up to its application, can not detect any precipitation.Electrode support 12 is placed on one inhales on (water) paper, utilize automatic pipette that a small amount of suspended substance is applied on the surface of the electrode support 12 that comprises fine particles then.When solution permeates by the electrode support of being made by the POROUS TITANIUM frit 12, form electrode 13 with continuous platinum layer form on the surface of electrode support 12.If desired, can for example improve the slickness on the surface that obtains thus by exerting pressure.In applying the replacement method of electrode 13, used water replaces SDS solution to make suspended substance, and this can reduce manufacturing cost.
Proton exchange (or proton transport) film 15 preferably has the form of sulfonation, fluoropolymer resin film, most preferably is the polymeric film Nafion of DuPont de Nemours company
The solid electrolyte that film 15 is formed according to ozone generating electrolysis cell of the present invention.In addition, film 15 also makes the gas delivery that produces in cathode side and anode side.The required water of electrolysis is introduced in a side of film 15 by second electrode support 12 that is provided with electrode 13, and the gaseous mixture of the oxygen that will handle and ozone is at the opposite side of film 15, promptly produce at ozone generating electrodes 16 places.It should be noted that by (being formed by film 15) on the electrode of making in the above described manner 13 provides very slick surface, because the deleterious deformation/distortion of the film 15 that the pressure that acts on by electrode structure 10 causes can be reduced to minimum possible degree.This helps to prolong the life-span according to ozone generating electrolysis cell of the present invention.
For the electrode support 17 that is used to support positive electrode 16, use precious metal (as platinum) or alloy and/or their mixture with good electrical conductivity.In electrolyzer according to the present invention, the platinum plate of suitably being bored a hole is as electrode support 17, and described platinum plate is provided with preferably diameter and is the through hole of 0.8mm at least.
Anode side supporting member 18 is used for and will removes from electrode 16 at the oxygen of electrode 16 places generation and the gaseous mixture of ozone during the cell operation.Supporting member 18 is used for electrode support 17 is fixed to electrode 16 and the latter is fixed to film 15 in addition, to provide ideal between them to electrically contact and uniform transitional surface is provided.In a preferred embodiment of the electrode structure shown in Figure 1A 10, supporting member 18 is made by the material of elasticity, porous, tool chemoresistance, is preferably made by the PTFE frit that obtains by high-pressure molding PTFE particulate.Supporting member 18 is provided with through hole 19.Be assembled into according to ozone generating electrolysis cell of the present invention in, through hole 19 is adapted to and is used to admit an anode side conductive members, this conductive members is used for anode side support 17 is electrically connected to outside DC power supply (see figure 2).
In electrolyzer according to the present invention, ozone generating electrodes 16 by have good electrical conductivity, plasticity-, high with respect to evolution or deposition potential superpotential and make for the material of the chemoresistance of the gaseous mixture of the oxygen of highly corrosive and ozone, preferably comprise by weight and to be the plumbic oxide of at least 10% PTFE and the mixture of PTFE.The mixture of plumbic oxide and PTFE does not use other additive to make by following process by solid-phase raw materials at ambient temperature.
On the plumbic oxide of a kind of component of the mixture of forming plumbic oxide and PTFE, the evolution or deposition potential of oxygen is very high, therefore can make the ozone of hope thereon with high transformation efficiency.Described component is favourable, because it is not expensive, can obtain, have unreactiveness usually (owing to not having the more oxidation state of high price) and dissolve in most of solvents, and has better electroconductibility than some metal.As everyone knows, at ozone between the emergence period, the oxygen that two kinds of possible crystal formation α of plumbic oxide and the crystal formation β among the β can be used for wishing-ozone transforms, wherein, between transition phase, as X-ray diffraction measure confirm, β type interface recrystallize (interfacial recrystallization) takes place.This means that need to change the plumbic oxide (that is, the recrystallize in reaction process) that is applied, this demonstrated a steady state value after 2-12 days cycles.Before making positive electrode 16, to rolling that plumbic oxide continues, obtain the colloid size thus, be that average particle size is the plumbic oxide particulate of 0.5-100 μ m that they make from the plumbic oxide fragment of initial macro-size.
For other component of electrode 16 materials, use to have the PTFE monofilament that fiber (cotton wool type) structure, thick 50-100 μ m and length are 1mm to the maximum.PTFE silk with described size can make by the shredder processing or the friction of PTFE piece spare.The size of initial PTFE monofilament has definite effect for the plasticity-and the elasticity of the mixture of final plumbic oxide and PTFE.
In order to make the material of positive electrode 16, plumbic oxide and PTFE a certain amount of, that for example be about the very thin monofilament form of 300mg a certain amount of, that for example be about the particulate that is rolled into the colloid size of 1600mg are put into a mixing tank.Described electrodeless (apolar) material can easily mix mutually.Stir slightly, after preferred 10 minutes, the mixture that obtains thus poured in the special frit shaping jig of preparing, and be pressed into inwards by applying the pressure that is at least 50MPa, is preferably 250MPa then for this reason, be the plate of 0.25mm with the thickness that formalizes.In moulding process, the PTFE silk takes place to tangle and merge, and makes the plumbic oxide particulate combined simultaneously.According to plumbic oxide/PTFE plate that microscopy obtains, prove that the material that obtains thus has compact size and successive surface, can easily form and have elasticity and ductility by mechanical means.At last, cut into the size of hope by the plumbic oxide/PTFE plate that will obtain thus and it is formalized make electrode 16.
Being noted herein that in the mixture of above-mentioned plumbic oxide and PTFE, is that a certain amount of PTFE of about 16% is being favourable aspect plasticity-/elasticity and the electroconductibility by weight.Utilizing under the situation of a large amount of PTFE, mixture will have more plasticity-, but have less electroconductibility.But under the situation that adds a small amount of PTFE, mixture will have less plasticity-, but have more electroconductibility.
Utilization rolls or other processing applies big shearing and makes PTFE stand thaumatropy, and---in our experience, this causes the stabilization to the β type crystal formation of plumbic oxide---is important.Because different with the method for prior art, the method according to this invention does not comprise heat treated step, therefore, can not change owing to deleterious crystal formation takes place for this.Rule of thumb, the conductivity of fiber electrode is significantly higher than the conductivity of the material with microgranular texture.
In the embodiment of above-mentioned electrode structure 10, positive electrode 16 and anode side electrode support 17 form isolating member.But, it should be noted that the ozone generating electrodes 16 and first electrode support 17 can form the electrode that combines, make thin platinum layer be applied on (outward) surface of the electrode of making by the mixture of plumbic oxide and PTFE 16.
When designing the structure of the electrolyzer of making by electrode structure 10 100, as shown in Figure 2, when selection is used for the material of electrolyzer 100, consider for the chemoresistance of the gaseous mixture of oxygen and ozone and the physical strength that is suitable for the pressure of the gas that brine electrolysis makes in the neutralization of its assembled state.Electrolyzer 100 is made up of cathode side half cell 110 and anode side half cell 115 under its assembled state, and they are fixed together in the mode of form fit and therefore sealing.Electrode structure 10 is provided with in present 140, and this seat is formed in the halfbody 110, and is limited by diapire and sidewall, wherein, and the supporting member 11 of described electrode structure 10 (seeing Figure 1A) on 140 the diapire of being present.The form fit butt is formed between the outside surface and seat 140 sidewall of pressure flange 145 of halfbody 115.Halfbody 115 is provided with the recess 148 of the anode side that is used to admit electrode structure 10, and wherein, described recess 148 is limited by pressure flange 145 along side direction.In the electrolyzer 100 that assembles, the supporting member 18 (shown in Figure 1A) of electrode structure 10 contacts closely with halfbody 115 in recess 148, and pressure flange 145 is pushed electrode structure 10 diapire of seat 140 to, thereby it is fixed firmly.
Cathode side half cell 110 is provided with and is used for admitting the through hole (not mark) in the accompanying drawings of discharging junctor 162 and cathode side electric connector case 130 to water connector 160, hydrogen and water in the mode of sealing.Anode side half cell 115 is provided with and is used for admitting ozone/oxygen gas to discharge the through hole of junctor 165 and anode side electric connector case 135 (not mark) in the accompanying drawings in the mode of sealing.Halfbody 110,115 by have chemoresistance, air-locked material is made, certain plastic material preferably, and preferably forming by injection molding or other manufacturing process.
Have at least one conductive member 150 (seeing Figure 1A) in electric connector case 130, electrical connection that provides between external power source and the negative potential 13 is provided for it.Conductive member 150 be a kind of can be along its longitudinal axis reversible deformation and the member of applied pressure thus; Described member 150 preferably has the form of column spring.It also is preferred that conductive member 150 is made of titanium.
Have at least one conductive member 155 (seeing Figure 1A) in electric connector case 135, electrical connection that provides between external power source and the electrode support 17 is provided for it.Conductive member 155 be a kind of can be along its longitudinal axis reversible deformation and the member of applied pressure thus; Described member 155 preferably has the form of column spring.It also is preferred that conductive member 155 is made by platinum.The conductive member 150,155 that use has the elastomeric element form makes it possible to eliminate because the dimensional variation that size deviation and temperature fluctuation cause.
The outer wall of halfbody 110,115, the wall that does not promptly contact with electrode structure 10 are respectively equipped with cathode side limiting plate 120 and anode side limiting plate 125.Limiting plate 120,125 is used to protect halfbody 110,125 to avoid outside mechanical effect.Therefore, limiting plate 120,125 is made, is preferably made by stainless steel by the material with high mechanical strength.Give water connector 160, hydrogen and water discharge junctor 162 and cathode side electric connector case 130 firmly (but releasedly) be fixed in the through hole (not shown) that is formed in the limiting plate 120.Similarly, ozone/oxygen gas discharge junctor 165 and anode side electric connector case 135 firmly (but releasedly) be fixed in the through hole that is formed in the limiting plate 125 (not mark) in the accompanying drawings.At last, for electrolyzer 100 is held in integral piece, sealing constitute electrolyzer 100 middle body electrode structure 10 and required electrically contacting and mechanical contact between the part of electrolyzer 100 (being shown specifically in Figure 1A) in halfbody 110,115 is provided, in being formed at halfbody 110,115 and in the through hole in limiting plate 120,125 tie-bolt 185 is set, described tie-bolt 185 is fastening by nut 190.
After making the said structure element, assemble according to electrolyzer 100 of the present invention by following step.At first, in-and-out bolt 185 is inserted in the through hole that is formed in the cathode side limiting plate 120, then, cathode side half cell 110 is arranged on the limiting plate 120, make its seat 140 up.Next, be provided with in present 140 and halfbody 110 position contacting places being contained in cathode side electrode support 12 in the supporting member 11 and negative potential 13.Then, electrode support is got wet, and will be cut off and the proton transmission film 15 of setting is placed on it, after this also described film is got wet by size.Subsequently, electrode 16 and the anode side electrode support 17 cut off by size and formalize are arranged on the film 15.Then, anode side supporting member 18 is placed on the electrode support 17, and anode side half cell 115 is pushed on the assembly that obtains thus, thereby make the different piece of electrode structure 10 fixing firmly.Next, supporting member 18 is got wet, limiting plate 125 is placed on the halfbody 115, and close mutually by nut 190 is screwed the structural element that forces electrolyzer 100 to in-and-out bolt 185, thus electrically contacting and mechanical contact and sealing engagement between the structural element is provided.At last, the coupling box 130,135 with junctor 160,162,165 and band conductive member 150,155 is installed in the electrolyzer 100.
At ozone generating electrolysis cell 100 on period according to the present invention, water is infeeded a side of the close negative potential 13 of electrolyzer 100, by porous cathode side electrode support 12 and porous negative electrode, current direction proton transmission film 15, and further flow to positive electrode 16 by film 15.When applying simultaneously when having the suitable polar dc voltage that is used for electrolyzer 100, the electrolysis of water begins at electrode 13,16 places, and positively charged hydrogen ion moves to negative potential 13 from positive electrode 16 by proton transmission film 15.Described hydrogen ion is by accepting to be transformed into from the electronics of negative potential 13 hydrogen of neutral charge.Simultaneously, produce oxygen and ozone owing to electrolysis and at positive electrode 16 places.The ozone transformation efficiency, promptly the amount of the ozone in the gaseous mixture that makes oxygen and ozone is by the quality of electrode 16 and working parameter decision.Can regulate amount and therefore its pressure of the gaseous mixture of the oxygen that produces under given conditions and ozone by changing Faradaic current.The amount of the ozone in the gaseous mixture of oxygen that produces by electrolyzer 100 according to the present invention and ozone is preferably by volume maximum 12%.
The current that utilization is introduced and partly shifted by junctor 162 by junctor 160 realize cooling off electrolyzer.It should be noted that on the anode side of electrolyzer 100 according to the present invention, water is shifted, because do not participate in electrolytic water and leave from anode side with the form of steam by the ejecta of junctor 165 and the gaseous mixture of oxygen and ozone from electrolyzer 100.
Claims (10)
1. an ozone generating electrolysis cell (10) comprising:
-negative potential (13);
-comprise the ozone generation positive electrode (16) of the mixture of lead (IV) oxide compound and polytetrafluoroethylene (PTFE);
-be arranged on the film (15) between the described negative, positive electrode (13,16); And
First electrode support (17) of the permeable conduction of-liquids and gases, one side contacts of this first electrode support and positive electrode (16) is positioned to relatively with described film (15), and the described side of described electrode support (17) has one and is coated with the surface that contains platinum layer, it is characterized in that
-described positive electrode (16) is made by a kind of mixture, has the plumbic oxide particulate of colloid size and PTFE silk that size is 1mm to the maximum prepares described mixture by high-pressure molding;
-described negative potential (13) is bonded on a side of described film (15) by a setting pressure, is positioned to relatively with positive electrode (16), and is formed on the surface of a porous second electrode support (12).
2. electrolyzer according to claim 1 is characterized in that, in described mixture, described PTFE silk has the thickness that is 100 μ m to the maximum.
3. electrolyzer according to claim 1 is characterized in that, described positive electrode (16) comprises and is at least a certain amount of PTFE of 10% by weight.
4. electrolyzer according to claim 1 is characterized in that, described positive electrode (16) is the mixture of moulding at ambient temperature.
5. electrolyzer according to claim 1 is characterized in that, described second electrode support (12) is with the particulate of electro-conductive material at ambient temperature and the frit of moulding in opening wide air.
6. electrolyzer according to claim 5 is characterized in that, described second electrode support (12) has the particle size gradient along depth direction, and wherein, the particulate of size minimum is arranged on negative potential (13) and locates.
7. electrolyzer according to claim 5 is characterized in that, the electro-conductive material of described second electrode support (12) is a titanium.
8. electrolyzer according to claim 7 is characterized in that, described negative potential (13) comprises at ambient temperature and be applied to platinum black on this negative potential with suspended substance in opening wide air.
9. electrolyzer according to claim 1 is characterized in that, described film (15) is the solid electrolyte film with proton transport performance.
10. electrolyzer according to claim 1 is characterized in that, described positive electrode (16) and first electrode support (17) form an integral unit jointly.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU0501204A HUP0501204A2 (en) | 2005-12-23 | 2005-12-23 | Ozone generating electrolytic cell |
| HUP0501204 | 2005-12-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101360848A true CN101360848A (en) | 2009-02-04 |
Family
ID=89986490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800516790A Pending CN101360848A (en) | 2005-12-23 | 2006-12-22 | Ozone generating electrolysis cell |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20080314740A1 (en) |
| EP (1) | EP1979509A2 (en) |
| JP (1) | JP2009520881A (en) |
| CN (1) | CN101360848A (en) |
| AU (1) | AU2006327902A1 (en) |
| HU (1) | HUP0501204A2 (en) |
| IL (1) | IL192391A0 (en) |
| NO (1) | NO20083195L (en) |
| RU (1) | RU2008129184A (en) |
| WO (1) | WO2007072098A2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102648308A (en) * | 2009-12-07 | 2012-08-22 | 氯工程公司 | Ozone generating apparatus |
| CN104278289A (en) * | 2013-07-11 | 2015-01-14 | 松下电器产业株式会社 | Electrolytic electrode device and electrolytic water generating device with the same |
| CN108301013A (en) * | 2018-02-14 | 2018-07-20 | 中氧科技（广州）有限公司 | A kind of preparation method for the modified anode of lead dioxide generating ozone |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU227638B1 (en) * | 2005-12-23 | 2011-10-28 | Thales Rt | Flowing laboratorial ozonizating apparatus and method for ozonization reaction |
| CN201746592U (en) * | 2010-06-22 | 2011-02-16 | 刘迅 | Water electrolysis device |
| WO2018178732A1 (en) | 2017-03-29 | 2018-10-04 | Rebek Laszlo | Device with improved characteristics to facilitate the production of ozone, instrument for the production of ozone equipped with a special device, and equipment for increasing the effectiveness of ozone treatment |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4976904A (en) * | 1989-04-20 | 1990-12-11 | Energy Research Corporation | Method and apparatus for continuous formation of fibrillated polymer binder electrode component |
| JP3080971B2 (en) * | 1990-08-01 | 2000-08-28 | ペルメレック電極株式会社 | Electrode structure for ozone production and method for producing the same |
| US6054230A (en) * | 1994-12-07 | 2000-04-25 | Japan Gore-Tex, Inc. | Ion exchange and electrode assembly for an electrochemical cell |
| JP3504021B2 (en) | 1994-12-08 | 2004-03-08 | ジャパンゴアテックス株式会社 | Electrode for electrochemical device and method for producing the same |
| US5529683A (en) * | 1995-03-20 | 1996-06-25 | United Technologies Corp. | Method for preventing degradation of membranes used in electrolytic ozone production systems during system shutdown |
| TW401373B (en) * | 1997-03-07 | 2000-08-11 | Univ Wuhan | Electrolytic ozone generating apparatus |
| JP2001181876A (en) * | 1999-12-22 | 2001-07-03 | Teeiku Wan Sogo Jimusho:Kk | Ozone generating electrolytic cell and its manufacturing method |
| WO2004015805A2 (en) * | 2002-08-09 | 2004-02-19 | Proton Energy Systems, Inc. | Electrochemical cell support structure |
-
2005
- 2005-12-23 HU HU0501204A patent/HUP0501204A2/en unknown
-
2006
- 2006-12-22 US US12/158,909 patent/US20080314740A1/en not_active Abandoned
- 2006-12-22 EP EP06831525A patent/EP1979509A2/en not_active Withdrawn
- 2006-12-22 CN CNA2006800516790A patent/CN101360848A/en active Pending
- 2006-12-22 RU RU2008129184/15A patent/RU2008129184A/en not_active Application Discontinuation
- 2006-12-22 WO PCT/HU2006/000126 patent/WO2007072098A2/en active Application Filing
- 2006-12-22 JP JP2008546654A patent/JP2009520881A/en active Pending
- 2006-12-22 AU AU2006327902A patent/AU2006327902A1/en not_active Abandoned
-
2008
- 2008-06-23 IL IL192391A patent/IL192391A0/en unknown
- 2008-07-17 NO NO20083195A patent/NO20083195L/en not_active Application Discontinuation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102648308A (en) * | 2009-12-07 | 2012-08-22 | 氯工程公司 | Ozone generating apparatus |
| CN102648308B (en) * | 2009-12-07 | 2014-07-02 | 培尔梅烈克电极股份有限公司 | Ozone generating apparatus |
| TWI484070B (en) * | 2009-12-07 | 2015-05-11 | Permelec Electrode Ltd | Ozone generation device |
| CN104278289A (en) * | 2013-07-11 | 2015-01-14 | 松下电器产业株式会社 | Electrolytic electrode device and electrolytic water generating device with the same |
| CN108301013A (en) * | 2018-02-14 | 2018-07-20 | 中氧科技（广州）有限公司 | A kind of preparation method for the modified anode of lead dioxide generating ozone |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007072098A2 (en) | 2007-06-28 |
| JP2009520881A (en) | 2009-05-28 |
| WO2007072098A3 (en) | 2007-12-13 |
| HU0501204D0 (en) | 2006-02-28 |
| US20080314740A1 (en) | 2008-12-25 |
| AU2006327902A1 (en) | 2007-06-28 |
| EP1979509A2 (en) | 2008-10-15 |
| NO20083195L (en) | 2008-09-11 |
| RU2008129184A (en) | 2010-01-27 |
| IL192391A0 (en) | 2009-08-03 |
| HUP0501204A2 (en) | 2007-07-30 |
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