CN104611719B - A kind of pure oxygen air source generator for synthesizing ozone - Google Patents
A kind of pure oxygen air source generator for synthesizing ozone Download PDFInfo
- Publication number
- CN104611719B CN104611719B CN201310542199.6A CN201310542199A CN104611719B CN 104611719 B CN104611719 B CN 104611719B CN 201310542199 A CN201310542199 A CN 201310542199A CN 104611719 B CN104611719 B CN 104611719B
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- power supply
- unit
- supply unit
- fuel cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 79
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 230000002194 synthesizing effect Effects 0.000 title abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000001257 hydrogen Substances 0.000 claims abstract description 84
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000000446 fuel Substances 0.000 claims abstract description 68
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 42
- 239000007789 gas Substances 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000002848 electrochemical method Methods 0.000 claims abstract description 5
- 238000011084 recovery Methods 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract 7
- 230000005611 electricity Effects 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004891 communication Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000008400 supply water Substances 0.000 claims 3
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 239000005518 polymer electrolyte Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229910006069 SO3H Inorganic materials 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- -1 plasma method Chemical compound 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Fuel Cell (AREA)
Abstract
A kind of pure oxygen air source generator for synthesizing ozone, uses electrochemical method that the pure oxygen feed unit of raw material, including at least two electrolysis water units and each self-corresponding power supply unit of each electrolysis water unit are provided for ozone generator；Power supply unit includes that at least one is used for Hydrogen Energy recovery power supply unit and an external power supply unit；It is independently connected on each power supply unit electrolysis water unit circuit only corresponding respectively；The hydrogen that all electrolysis water units are produced is delivered to hydrogen fuel cell as fuel；The feed(raw material)inlet that the oxygen that electrolysis water unit is produced is delivered to ozone generator produces ozone；Hydrogen Energy reclaims the negative pole of the hydrogen fuel cell of power supply unit, side of the positive electrode difference inputting hydrogen and air, and the hydrogen that it is input into is connected by pipeline with the cathode hydrogen air chamber of electrolysis water unit, and the discharge gas of its side of the positive electrode is emptied after gas-liquid separation.The present invention is indoors, outdoor and field place is equal can prepare high-purity oxygen for ozone generator by air low cost, steady and continuous.
Description
Technical field
The present invention relates to a kind of pure oxygen air source generator, especially a kind of pure oxygen air source generator for synthesizing ozone.
Background technology
Ozone is a kind of unstable gas of strong oxidizing property, easily decomposes and cannot store, therefore scene is needed when actually used
Produce, i.e., with system with.The synthesis of ozone, usually with oxygen-containing gas（Such as pure oxygen and air）It is source of the gas, by plasma
（Dielectric barrier discharge or corona discharge are produced）Or oxygen molecule is dissociated into oxygen atom by ultraviolet light, subsequent oxygen atom leads to oxygen molecule
Cross three-body collision reaction generation ozone.Synthesize the commercial methods of ozone, mainly plasma method, its is most widely used.
Because the raw material for synthesizing ozone is that power consumption and concentration influence of the oxygen content on ozone is notable in oxygen, therefore source of the gas.It is with air
Ozone power consumption during source of the gas, more than 2 times when at least with pure oxygen as source of the gas.Ozone concentration during with air as source of the gas can only reach
To 3-6wt%, during far below with pure oxygen as source of the gas（Up to 15wt%）.In addition, during plasma method synthesis ozone, if with sky
Gas or oxygen-enriched air are source of the gas, inevitably produce oxynitrides（NOx）Deng harmful and corrosive gas；If being with pure oxygen
Source of the gas, only has ozone and oxygen in its gas, composition is pure, has no toxic side effect.
At present, the pure oxygen air source generator of ozone is synthesized, it is main to use molecular sieve pressure-variable adsorption（PSA）Technology.It is this pure
Oxygen source generator, need to pre-process moisture and carbon dioxide in removing raw air, and adsorbent bed is more, and technological process is complicated, body
Product is huge, and reliability is poor, and the purity of acquisition oxygen is not high, and its oxygen concentration only up to reach 95%.With solid electricity
During solution matter water electrolysis technology is the electrolysis water of representative, the anode and negative electrode of electrolytic cell can acquisition pure oxygens and pure simultaneously respectively
Hydrogen, its purity may be up to more than 99.99%.Solid electrolyte cell operation current density is high（1-3A/cm2）, the safe and reliable longevity
Life length（Electrolyte is not required to, pure water is only needed）, energy efficiency is up to more than 85%, and electrolyser construction is compact, small volume, lightweight.But
The power consumption that solid electrolyte electrolysis water prepares pure oxygen is higher, and every cubic metre of oxygen need to consume 8-10 degree electricity.In addition, cathode of electrolytic tank
If the hydrogen of generation is not used, Hydrogen Energy is not only wasted, and there is inflammable and explosive potential safety hazard.
For the problem of above-mentioned hydrogen, Chinese invention patent 02114162.2 and 201110105892.8 is by electrolytic cell and hydrogen
Fuel cell is combined.The hydrogen that electrolytic cell is produced, flows into hydrogen fuel cell and generates electricity.Chinese invention patent 02114162.2, by hydrogen
Fuel cell with the direct current obtained by external 220V AC rectifications as dual power supply, while being powered to electrolytic cell.In double electricity
In source circuit, if the voltage of external power supply is higher than the operating voltage of fuel cell, fuel cell is then damaged by reverse charge.And because
The factor such as unstability of electrolytic cell load, thus be difficult to ensure that in actual use the two-supply circuit can it is reliable and stable and
High-efficiency operation.Further, since often the electric energy that hydrogen fuel cell is reclaimed, only about account for the 30-40% that electrolytic cell consumes electric energy, i.e.,
Cubic meter oxygen still needs to consumption 5-7 degree electricity, and the operating cost for preparing pure oxygen is still higher；Furthermore, the patent is only applicable to can
The place of 220V alternating currents is provided.Chinese invention patent 201110105892.8 limits to solve two-supply circuit and field of employment
Property problem, powered to electrolytic cell using secondary cell, hydrogen fuel cell in the way of floating charge give secondary cell charge.But due to
Restricting for water consumption problem higher is limited and is electrolysed by secondary power supply capacity, therefore the limited electric energy of secondary cell storage is being transported
To quickly be consumed during row, operation is necessarily required to external power after a period of time charge can just rework.The patent system oxygen is filled
Put, if as the pure oxygen air source generator of synthesis ozone, can only low discharge and short time interval generation pure oxygen.
The content of the invention
The present invention is in order to solve the above-mentioned technical problem existing for prior art, there is provided a kind of pure oxygen source of the gas of synthesis ozone
Generator, indoors, outdoor or field place can for ozone generator by air it is inexpensive, prepare high-purity to steady and continuous
Oxygen.
Technical solution of the invention is：A kind of pure oxygen air source generator for synthesizing ozone, using electrochemical method point
Pure oxygen is prepared from air, especially fuel cell and electrolysis water technology is combined and is prepared pure oxygen, for ozone generator provides pure oxygen
Feed unit.
The pure oxygen feed unit includes at least two electrolysis water units and each self-corresponding power supply of each electrolysis water unit
Unit；
Power supply unit includes that at least one is used for Hydrogen Energy recovery power supply unit and an external power supply unit, and Hydrogen Energy is reclaimed and supplied
Electric unit uses hydrogen fuel cell, external power supply unit to select solar cell, DMFC, external communication power network
At least one in power supply；
Described electrolysis water unit is water electrolytic cell；
It is independently connected on each power supply unit electrolysis water unit circuit only corresponding respectively；
The hydrogen that all electrolysis water units are produced is converged by Hydrogen Line, and hydrogen fuel cell is delivered to together as combustion
Material；The oxygen that each electrolysis water unit is produced is converged by oxygen channel and flows into drier, is delivered to ozone hair after drying together
The raw material oxygen intake of raw device produces ozone；
Hydrogen Energy reclaims the negative pole of the hydrogen fuel cell of power supply unit, side of the positive electrode difference inputting hydrogen and air, and it is input into
Hydrogen be connected with the cathode hydrogen air chamber of electrolysis water unit by pipeline, the discharge gas of side of the positive electrode is emptied after gas-liquid separation.
Described electrolysis water unit, its anode and negative electrode are separated by electrolyte membrance, respectively with the positive pole of power supply unit and
Negative pole is connected.Electrolyte membrance can be acid and/or alkaline polymer electrolyte membrane, or acid, the electricity of alkali steeping porous septum
Solution matter barrier film.In acid system or alkaline system, proton hydrate or hydroxide ion pass through electrolyte under internal electric field effect
Barrier film migrates the generation for having oxygen to cathode side generation hydrogen, anode-side.Electrolyte membrance can be with acid perfluorinated sulfonic acid
Resin, sulfonated polyether-ether-ketone or SPSF are the polymer electrolyte and/or the quaternized polysulfones with alkalescence of representative
(Shanfu Lu,et al.PNAS2008,105,20611;Junfeng Zhou,etal.Journal of Power
Sources2009,190,285) be representative polymer electrolyte.The catalytic active component of electrocatalyst for cathode is tool
There is the Pt of evolving hydrogen reaction function black or Pt/C, catalytic active component is 0.01-1mg/cm in the load amount of membrane electrode2；Anode electricity is urged
Agent catalytic active component is by one or more the metal or its oxygen in the transition metal of periodic table of elements group VIII
Compound constitutes (Chinese patent CN101008087B), and catalytic active component is 0.01-4mg/cm in the load amount of membrane electrode2。
Described hydrogen fuel cell power supply unit, its positive pole and negative pole are separated to form two air chambers by electrolyte membrance.It is negative
Pole side air chamber is connected with Hydrogen Line, flows into the hydrogen that electrolysis water unit is produced；Side of the positive electrode air chamber is by fan or air pump by air
Feeding, the oxygen needed for obtaining hydrogen fuel cell.Side of the positive electrode air chamber discharge gas is emptied (reference can be made to Chinese patent after gas-liquid separation
Application：Zhu Xiaobing, Zhu Weikun, Zhu Aimin, a kind of Liu Jinglin " electrochemistry side by preparing pure oxygen and Poor oxygen gas containing oxygen gas mixture
Method ").Side of the positive electrode produce water with discharge gas flow into gas-liquid separator, after gas-liquid separation water be back to electrolytic cell negative electrode and/or
Anode, recycles.If disregarding the loss of the water that volatilization or evaporation factor are brought, water need not be added additionally.This is not only
The weight of device is alleviated, the cost of pure water is used when even more greatly reducing operation.Electrolyte membrance can be it is acid and/or
Alkaline polymer electrolyte membrane, or acid, the electrolyte membrance of alkali steeping porous septum.Electrolyte membrance can be with the complete of acidity
Perfluorosulfonic acid resin, sulfonated polyether-ether-ketone or SPSF are the polymer electrolyte of representative and/or are gathered with the quaternized of alkalescence
Sulfone (Shanfu Lu, et al.PNAS2008,105,20611;Junfeng Zhou,etal.Journal of Power
Sources2009,190,285) be representative polymer electrolyte.The catalytic active component of negative pole elctro-catalyst is tool
There is the Pt of hydroxide reaction function black or Pt/C, catalytic active component is 0.01-1mg/cm in the load amount of membrane electrode2；Positive pole electricity
Catalyst activity component by one or more the metal in the transition metal of periodic table of elements group VIII or its
Oxide constitutes (Chinese patent CN101008087B), and catalytic active component is 0.01-4mg/cm in the load amount of membrane electrode2。
Described circuit connection, the negative pole of the negative electrode of its electrolytic cell, anode and fuel cell, positive pole are connected.
Described master unit is made up of fuel cell and electrolytic cell, described auxiliary unit by hydrogen make-up function electrolysis
Pond constitutes.There was only gas circuit connection between described master unit and auxiliary unit, there is no circuit to connect.The cathodic hydrogen gas of electrolytic cell
Road is connected with fuel cell anode hydrogen gas circuit.The oxygen of the anode discharge of electrolytic cell after dried process, send out by input to ozone
Raw device unstripped gas entrance, produces ozone output.
Described DMFC power supply unit, negative pole is flowed into using methyl alcohol as fuel, is with oxygen-containing gas
Oxidant flows into positive pole, and generate electricity supply electrolytic cell.
Described solar cell for supplying power unit, directly using the solar energy with voltage needed for water electrolytic cell and power match
Battery commercially produced product, generate electricity supply electrolytic cell.
Described AC network power supply unit, directly using the AC network with voltage needed for water electrolytic cell and power match
The dc source commercially produced product of power supply, generate electricity supply electrolytic cell.
Place prepares pure oxygen for ozone generator indoors, and because AC network is easy to connect, preferred external power supply is single
Unit is dc source simultaneously using solar cell and external AC net.This can both save electric energy, reduce operating cost, and
The uncontrollable shortcoming of solar energy can be made up.
In outdoor and field place for ozone generator prepares pure oxygen, because AC network is inconvenient or is difficult to connect, preferably
External power supply unit be simultaneously use solar cell and DMFC.This had both given full play to outdoor and field
Obtain solar energy advantage, can make up again solar energy it is uncontrollable and inconvenient or be difficult to connection AC network shortcoming.
A kind of pure oxygen air source generator of synthesis ozone that the present invention is provided, is prepared pure using electrochemical method separation air
Oxygen, fuel cell and electrolysis water technology are especially combined prepare pure oxygen.Using at least two electrolysis water units and each of which
Power supply unit, stable and reliable operation；Hydrogen Energy reclaims the Hydrogen Energy that power supply unit has recycled electrolysis water generation, has saved the energy
And solve the safety problem of hydrogen.It is employed as while solar cell is with AC network or with DMFC
External power supply unit, not reduce further power consumption merely with solar energy, and indoors, outdoor can be smelly with field place
Oxygen Generator continuous-stable prepares pure oxygen.
The present invention is as follows for the advantage that ozone generator prepares the method for pure oxygen：
1. the method that traditional solid electrolyte electrolysis water prepares pure oxygen, its power consumption is higher, and every cubic metre of oxygen needs consumption
8-10 degree electricity.If in addition, the hydrogen that cathode of electrolytic tank is produced is not used, not only wasting Hydrogen Energy, and exist inflammable
Explosive potential safety hazard.Relative to conventional method, this patent method can recycle hydrogen hair using electrolysis water oxygen simultaneously
Electricity supply electrolytic cell produces more oxygen, and energy efficiency is higher, and electrolysis aquatic products hydrogen and fuel cell consume hydrogen, nothing in system
Net hydrogen generation, system uses safer.
2. Chinese invention patent 02114162.2, by hydrogen fuel cell and the direct current obtained by external 220V AC rectifications
Electricity as dual power supply, while being powered to electrolytic cell.In two-supply circuit, if the voltage of external power supply is higher than the work of fuel cell
Make voltage, fuel cell is then damaged by reverse charge.The factors such as the unstability for being loaded by electrolytic cell again, therefore actually used
In be difficult to ensure that the two-supply circuit being capable of reliable and stable and high-efficiency operation.Further, since the electric energy that hydrogen fuel cell is reclaimed,
Only about account for the 30-40% that electrolytic cell consumes electric energy, i.e., every cubic metre oxygen still needs to consumption 5-7 degree electricity, prepare the operation of pure oxygen into
This is still higher；Furthermore, the patent is only applicable to provide the place of 220V alternating currents.Relative to Chinese patent
02114162.2, the method for this patent, using independent on each power supply unit electrolysis water unit circuit only corresponding respectively
Connection.External power supply unit is from solar cell, DMFC, these three batteries of AC network or power supply
It is at least one.This patent method is suitable indoors, outdoor can continuously and stably for ozone generator provides pure with field place
Oxygen.
3. Chinese invention patent 201110105892.8 is adopted to solve the problems, such as two-supply circuit and field of employment limitation
Powered to electrolytic cell with secondary cell, hydrogen fuel cell is charged in the way of floating charge to secondary cell.But due to by secondary power supply
The limitation of capacity and the restriction of electrolysis water consumption problem higher, therefore the limited electric energy of secondary cell storage in the process of running will
Quick consumption, operation is necessarily required to external power after a period of time charge can just rework.The patent oxygenerator is only suitable for small
Flow and short time interval are used.This patent method, volume is produced using external power supply unit with auxiliary unit associated with electrolytic cell
Outer hydrogen come supplement fuel cell for its generate electricity, to make up the energy loss of master unit associated with fuel cell and electrolytic cell,
Rather than by secondary cell come electric energy supplement making up energy loss.Chinese invention patent 201110105892.8 receives secondary cell
Store energy capacity limitation, there is provided be limited capacity or batch (-type) method for producing oxygen through.This patent be adapted to indoors, it is outdoor with
Field place energy continuous-stable provides pure oxygen for ozone generator.
Brief description of the drawings
The gas circuit annexation of described Fig. 1 is as follows：Master unit is made up of fuel cell FC and electrolytic cell WE-1, and auxiliary is single
Unit be made up of the electrolytic cell WE-2 and external power supply unit of hydrogen make-up function, its external power supply unit using solar cell,
At least one of DMFC, dc source of AC network.Between described master unit and auxiliary unit only
Gas circuit is connected, and does not have circuit to connect.The cathodic hydrogen gas circuit of electrolytic cell WE-1 and WE-2 and fuel cell FC negative pole hydrogen gas circuits
Connection.The exhaust of the anode-side of electrolytic cell WE-1 and WE-2 obtains pure oxygen gas after drier.Pure oxygen gas subsequently input to
Ozone generator feed(raw material)inlet, produces ozone.The side of the positive electrode input air of fuel cell FC.The side of the positive electrode exhaust of fuel cell FC
Mouth is connected with the gas-liquid separator of water storage unit, and discharge gas is directly emptied after gas-liquid separation, and water is back to master unit electrolytic cell
The anode-side of WE-1 and auxiliary unit electrolytic cell WE-2, recycles.Due to the inevitable factor of water evaporation, toward water storage list
The separator of unit adds suitable quantity of water to maintain the material balance of the water of whole system.
The circuit connecting relation of described Fig. 1 is as follows：Negative pole, the positive pole of fuel cell FC respectively with the moon of electrolytic cell WE-1
Pole, anode connection.Negative pole, the positive pole of the dc source of external power supply unit negative pole respectively with electrolytic cell WE-2, positive pole are connected.
A kind of flow charts for using electrochemical method that pure oxygen is provided for ozone generator of Fig. 1.FC, WE-1 are respectively in figure
The fuel cell FC of master unit, electrolytic cell WE-1；WE-2 is the electrolytic cell WE-2 of auxiliary unit；Water-gas Separator
It is the gas-liquid separator of water storage unit；Solar Cell and/or DMFC and/or DC power are the external of auxiliary unit
At least one in the solar cell of power supply, DMFC, these three batteries of AC network or power supply；03-
Generator is ozone generator；The AIR and H of system input2O is respectively the air and water of input, the Vent and O of output3Point
It is not air-discharging and ozone.
By taking air as an example, the external power supply unit of auxiliary unit is connected generation hydrogen with electrolytic cell WE-2 to Fig. 1, supplies main list
First fuel cell FC makes its continuous normal operation to start whole system and make up the energy consumption of master unit.Its external power supply unit can
From at least one in solar cell, DMFC, these three batteries of AC network or power supply.Master unit
Fuel cell FC negative poles and positive pole separately flow into hydrogen and air, and generate electricity supply master unit electrolytic cell WE-1, by being electrolysed aquatic products
Raw hydrogen circulates supply fuel cell again, forms hydrogen and recycles.
The eluting gas of the side of the positive electrode of fuel cell FC after gas-liquid separator by emptying.The sun of electrolytic cell WE-1, WE-2
The eluting gas of pole side is input into ozone generator 0 by drier3- Generator feed(raw material)inlets, produce ozone.
The water that fuel cell FC side of the positive electrode is produced flows into gas-liquid separator with discharge gas, and water is back to electrolysis after gas-liquid separation
The anode-side in pond, recycles.If disregarding the loss of the water that volatilization or evaporation factor are brought, water need not be added additionally.
In view of the loss that inevitable gas circuit water evaporation brings, water can be suitably supplemented toward water storage unit.
The thus input of whole system is supplied with the air of the fuel cell FC of master unit, supplements water evaporation loss
Water；Output is ozone generator 03Ozone, the fuel cell FC side of the positive electrode eluting gas that-Generator is produced are through gas-liquid separation
The gas for emptying afterwards.
Specific embodiment
Embodiment 1
Take Nafion212 films（EW=1052g/molSO3H）40cm2, add the METHYLPYRROLIDONE and 10ml of 20ml
Isopropanol heating for dissolving perfluorinated sulfonic acid solution is obtained.By perfluorinated sulfonic acid solution curtain coating on flat board, heated 10 hours at 70 DEG C,
It is warming up to 77 DEG C again to heat 12 hours, after solvent volatilizees substantially, 130 DEG C are heat-treated 1 hour into basilar memebrane in vacuum drying oven, system
Standby thickness is 18 μm of polymer electrolyte membrane for fuel cell and 50 μm of solid electrolyte water electrolytic cell films.
Using SGL carbon papers, ptfe emulsion, XC-72 carbon dusts, 5%（E.I.Du Pont Company）Solution and 20%
Pt/C catalyst preparation electrodes, whereinResin is 0.8 with the mass ratio of C.Negative pole Pt loads amount is 0.3mg/cm2, positive pole
Pt loads amount is 0.5mg/cm2.Compacting 5cm2The operating condition of the three-in-one hydraulic presses of MEA be, 160 DEG C, minute-pressure precompressed 1 minute,
Pressure to 2MPa is improved again, and hot pressing 2 minutes, cooling obtains final product fuel cell MEA.
Using SGL carbon papers, ptfe emulsion, XC-72 carbon dusts, 5%（E.I.Du Pont Company EW=1100g/mol-
SO3H）Solution and negative electrode 20%Pt/C catalyst, anode are with Pt is black, IrO2Catalyst prepares electrode respectively.Negative electrodeResin is 0.8 with the mass ratio of C.The Pt of anode is black, IrO2Powder and Nafion resins（EW=1100g/mol-SO3H）
With mass ratio be 5:1.Catalyst,Resin solution adds isopropanol to be made into anode after 12 hours through ultrasonic disperse and urges
Change the standby slurry of layer.Negative electrode Pt loads amount is 0.3mg/cm2, anode Pt loads amount is 4mg/cm2.Compacting 5cm2The three-in-one oil of MEA
The operating condition of press is, 160 DEG C, minute-pressure precompressed 1 minute, then improves pressure to 2MPa, hot pressing 2 minutes, and cooling obtains final product solid
Electrolyte water electrolysis pond MEA.
The evaluating of fuel cell is as follows：The H of dry state2/AIR；Operating pressure normal pressure；30~80 DEG C of operation temperature；
mPt,MEA=0.7mg/cm2；Single pond test；Hydrogen is recycled, and air velocity is 100ml/min；Effective area is 5cm2。
The evaluating of electrolytic cell is as follows：Water electrolytic cell temperature is 45 DEG C, normal pressure, water-carrying capacity 15ml/min, single pond test,
Effective area is 5cm2.Powered using MPS30 DC current stabilized power supplies.
Whole system flowage structure as shown in figure 1, after stable operation 2 hours, the Current Voltage output data such as table 1 of measure
It is shown.Whole system air is input into 100ml/min, while supplementing water 10ml/ days；It is input into the pure oxygen of ozone generator
20ml/min, it is the ozone of 14wt% to produce concentration.
The electrochemistry experiment data of the embodiment 1 of table 1.
The method that the present invention prepares pure oxygen for ozone generator, using at least two electrolysis water units and their own confession
Electric unit, continuous stable and reliable operation；Hydrogen Energy reclaims the Hydrogen Energy that power supply unit has recycled electrolysis water generation, has saved the energy
And solve the safety problem of hydrogen；
External power supply unit is employed as while solar cell is with AC network or with DMFC, no
Reduce further power consumption merely with solar energy, and indoors, it is outdoor can be that ozone generator is continuously steady with field place
Surely pure oxygen is prepared.
For the electrolytic cell that the operation energy consumption solved the problems, such as between fuel cell and electrolytic cell, the present invention pass through auxiliary unit
To the negative side of master unit fuel cell, this hydrogen make-up passes through fuel cell power generation to the hydrogen make of cathode side, to make up master
Operation energy loss between the fuel cell and electrolytic cell of unit.And Chinese invention patent 02114162.2 is electric by hydrogen fuel
Pond with the direct current obtained by external 220V AC rectifications as dual power supply, while powering to make up above-mentioned energy to electrolytic cell
, there are two (1) if the operating voltage of the voltage higher than fuel cell of external power supply, fuel cell is then by reverse charge in consumption
Damage；(2) factors such as the unstability and because of electrolytic cell load, therefore the two-supply circuit energy is difficult to ensure that in actual use
Enough reliable and stable and high-efficiency operations.Therefore this patent is made up between fuel cell and electrolytic cell by the method for hydrogen make-up
Energy loss method, avoid making fuel cell reverse charge with two advantages (1) and damage；(2) the fuel electricity of master unit
As single power supply for electrolytic cell is powered, it has reliable and stable and high-efficiency operation circuit in pond.
Claims (8)
1. it is a kind of synthesize ozone pure oxygen air source generator, it is characterised in that electrochemical method is used, for ozone generator is provided
The pure oxygen feed unit of raw material,
The pure oxygen feed unit includes at least two electrolysis water units and each self-corresponding power supply unit of each electrolysis water unit；
Power supply unit includes that at least one is used for Hydrogen Energy recovery power supply unit and an external power supply unit, and it is single that Hydrogen Energy reclaims power supply
Unit uses hydrogen fuel cell, external power supply unit to select solar cell, DMFC, external communication electric network source
In at least one；
Described electrolysis water unit is water electrolytic cell；
It is independently connected on each power supply unit electrolysis water unit circuit only corresponding respectively；
The hydrogen that all electrolysis water units are produced is converged by Hydrogen Line, and hydrogen fuel cell is delivered to together as fuel；Often
The oxygen that individual electrolysis water unit is produced is converged by oxygen channel and flows into drier, and ozone generator is delivered to together after drying
Raw material oxygen intake produces ozone；
Hydrogen Energy reclaims the negative pole of the hydrogen fuel cell of power supply unit, side of the positive electrode difference inputting hydrogen and air, its hydrogen being input into
Gas is connected by pipeline with the cathode hydrogen air chamber of electrolysis water unit, and the discharge gas of side of the positive electrode is emptied after gas-liquid separation；
Master unit is constituted by least one hydrogen fuel cell and water electrolytic cell；
By at least one water electrolytic cell as auxiliary unit, electrically connected with external power supply unit, for being provided for hydrogen fuel cell
Hydrogen make-up；
Described master unit, auxiliary unit only has therebetween gas circuit connection, does not have circuit to connect；The cathodic hydrogen of water electrolytic cell
Gas circuit is connected with fuel cell anode hydrogen gas circuit.
2. according to the pure oxygen air source generator of the synthesis ozone described in claim 1, it is characterised in that：
The anode and negative electrode of described electrolysis water unit are separated by electrolyte membrance, respectively with the positive pole and negative pole phase of power supply unit
Even.
3. according to the pure oxygen air source generator of the synthesis ozone described in claim 1, it is characterised in that：
Described hydrogen fuel cell power supply unit, its positive pole and negative pole are separated to form two air chambers by electrolyte membrance；Negative side
Air chamber is connected with Hydrogen Line, flows into the hydrogen that electrolysis water unit is produced；Side of the positive electrode air chamber is sent into air by fan or air pump,
Oxygen needed for obtaining hydrogen fuel cell；Side of the positive electrode air chamber discharge gas is emptied after gas-liquid separation.
4. according to the pure oxygen air source generator of the synthesis ozone described in claim 1 or 3, it is characterised in that：
The water that hydrogen fuel cell side of the positive electrode is produced flows into gas-liquid separator with discharge gas, water backflow supply electrolytic cell after gas-liquid separation
Negative electrode and/or anode, recycle.
5. according to the pure oxygen air source generator of the synthesis ozone described in claim 1, it is characterised in that：
Described circuit connection, negative electrode, the anode of its electrolysis water unit electrolytic cell negative pole, positive pole phase respectively with hydrogen fuel cell
Even.
6. according to the pure oxygen air source generator of the synthesis ozone described in claim 1, it is characterised in that：
Described DMFC power supply unit, negative pole is flowed into using methyl alcohol as fuel, is oxidation with oxygen-containing gas
Agent flows into positive pole, and generate electricity supply water electrolytic cell；
Or, described solar cell for supplying power unit, directly using the solar energy with voltage needed for water electrolytic cell and power match
Battery commercially produced product, generate electricity supply water electrolytic cell；
Or, described AC network power supply unit, directly using the AC network with voltage needed for water electrolytic cell and power match
The dc source commercially produced product of power supply, generate electricity supply water electrolytic cell.
7. according to the pure oxygen air source generator of the synthesis ozone described in claim 1, it is characterised in that：
Preferred external power supply unit be solar cell with AC network or with DMFC while use.
8. according to the pure oxygen air source generator of the synthesis ozone described in claim 1, it is characterised in that：
Connected one to one on circuit between the hydrogen fuel cell and water electrolytic cell that constitute master unit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310542199.6A CN104611719B (en) | 2013-11-05 | 2013-11-05 | A kind of pure oxygen air source generator for synthesizing ozone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310542199.6A CN104611719B (en) | 2013-11-05 | 2013-11-05 | A kind of pure oxygen air source generator for synthesizing ozone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104611719A CN104611719A (en) | 2015-05-13 |
| CN104611719B true CN104611719B (en) | 2017-07-11 |
Family
ID=53146355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310542199.6A Active CN104611719B (en) | 2013-11-05 | 2013-11-05 | A kind of pure oxygen air source generator for synthesizing ozone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104611719B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102015220424A1 (en) * | 2015-10-20 | 2017-04-20 | Robert Bosch Gmbh | Disinfecting device, method for disinfecting household appliances and use of a disinfecting device |
| CN117418247B (en) * | 2023-12-18 | 2024-03-15 | 中国科学院生态环境研究中心 | Ozone generating device and method for electrochemical coupling oxygen dissociation |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1265025C (en) * | 2002-05-30 | 2006-07-19 | 谌冠卿 | Oxygen production device |
| US20060088739A1 (en) * | 2004-10-26 | 2006-04-27 | Energy Conversion Devices, Inc. | Power generation and supply system |
| US20080226954A1 (en) * | 2007-03-16 | 2008-09-18 | Samsung Electro-Mechanics Co., Ltd. | Hydrogen generating apparatus, fuel cell power generation system, method of controlling hydrogen generating quantity and recorded medium recorded program performing the same |
| CN101565832A (en) * | 2008-04-25 | 2009-10-28 | 清华大学 | Water electrolysis hydrogen production system for solar battery |
-
2013
- 2013-11-05 CN CN201310542199.6A patent/CN104611719B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104611719A (en) | 2015-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9574276B2 (en) | Production of low temperature electrolytic hydrogen | |
| CN110791774B (en) | Method for producing hydrogen by electrolyzing water vapor | |
| Qian et al. | Architecture for portable direct liquid fuel cells | |
| CN101306302B (en) | Hydrogen containing industrial waste gas separation and purification method | |
| Tolmachev | Hydrogen-halogen electrochemical cells: A review of applications and technologies | |
| NO343985B1 (en) | Polymer electrolyte membrane (PEM) water electrolyser cell, stack and system and a method for producing hydrogen in said PEM water electrolyser system | |
| CN103178283B (en) | Hydrogen-bromine energy storage battery structure | |
| WO2023246669A1 (en) | Fuel cell power generation system and control method therefor | |
| US10017865B2 (en) | Electrochemical method for producing pure-oxygen gas and oxygen-lean gas from oxygen-containing gas mixtures | |
| Cai et al. | Design and simulation of a liquid electrolyte passive direct methanol fuel cell with low methanol crossover | |
| CN104611719B (en) | A kind of pure oxygen air source generator for synthesizing ozone | |
| CN101325266A (en) | Power supply system for minisize composite regenerative fuel battery | |
| CN102456903A (en) | Method for electrolytically preparing hydrogen from formic acid | |
| CN106532087A (en) | Fuel power battery electricity generator and electricity generation method | |
| CN210736904U (en) | Ammonia electrolysis hydrogen production system | |
| CN104611717B (en) | A kind of by the electrochemical method preparing pure oxygen and Poor oxygen gas containing oxygen gas mixture | |
| US20070190378A1 (en) | Direct oxidation fuel cell systems with regulated fuel concentration and oxidant flow | |
| CN108390083A (en) | A kind of composite regenerative fuel battery system discharge operating mode startup method | |
| EP4386914A1 (en) | Electrochemical cell, power generation method using electrochemical cell, and method for producing hydrogen gas using electrochemical cell | |
| JPS63237363A (en) | Methanol fuel cell | |
| CN206516707U (en) | Fuels and energy cell power generator | |
| CN118299626A (en) | Fuel cell power generation-water electrolysis hydrogen production integrated system | |
| CN117070971A (en) | PEM water electrolysis hydrogen production electrolytic cell and hydrogen production method thereof | |
| Liang et al. | Research on full-process model of fuel cell generation system | |
| US20100221625A1 (en) | Low-porosity anode diffusion media for high concentration direct methanol fuel cells and method of making |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |