CN102403523A - Apparatus and method for processing organic wastewater by using TiO2-based photocatalytic composite-electrode fuel cell - Google Patents
Apparatus and method for processing organic wastewater by using TiO2-based photocatalytic composite-electrode fuel cell Download PDFInfo
- Publication number
- CN102403523A CN102403523A CN2011102733766A CN201110273376A CN102403523A CN 102403523 A CN102403523 A CN 102403523A CN 2011102733766 A CN2011102733766 A CN 2011102733766A CN 201110273376 A CN201110273376 A CN 201110273376A CN 102403523 A CN102403523 A CN 102403523A
- Authority
- CN
- China
- Prior art keywords
- light anode
- photocathode
- anode
- organic wastewater
- tio
- 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.)
- Granted
Links
Images
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
- Y02E60/50—Fuel cells
Landscapes
- Catalysts (AREA)
Abstract
The invention provides two TiO2-based photocatalytic composite-electrode fuel cells with different structures, and an apparatus used for processing organic wastewater. The apparatus comprises a speed regulator, a driving motor, a photocathode shaft, a photocathode rotary table, plural sheets of photo-anodes, a fuel cell reaction tank, and an excitation light source. The apparatus is characterized in that: a draft-tube is arranged on the bottom of the fuel cell reaction tank; and a water pump is arranged on the draft-tube. The water pump is started; the organic wastewater is transferred from the draft-tube on the bottom of the photo-anode reaction tank to the top of the photo-anodes, and flows down, such that a liquid film is formed on the surfaces of the photo-anodes; meanwhile, the driving motor is started, the rotation speed of the photocathode rotary table is controlled by the speed regulator, such that the photocathode rotary table rotates, and a liquid film is also formed on the surface of the photocathode. Photo-anodes with different structures are adopted, such that the processing efficiency of the organic wastewater is improved. The photo-anodes are designed as rectangles, such that the liquid film formed by the water flow on the surfaces of the photo-anodes is more uniform, and the organic wastewater can be more effectively processed by using the TiO2-based photocatalytic composite-electrode fuel cell.
Description
Technical field
What the present invention relates to is the system of a kind of energy, chemical industry, environmental area processing organic wastewater.Specifically be a kind of TiO
2Base optic catalytic combination electrode fuel cell is handled the apparatus and method of organic wastewater.
Background technology
Fuel cell is a kind of device that can directly the chemical energy of fuel be changed into electric energy.From 1838; C. F.
has found the electrochemical effect of fuel cell and has stressed can produce since this phenomenon of electric current in the chemical reaction process that chlorine or oxygen carried out on hydrogen and the platinum electrode for the first time; The researcher has carried out extensive and deep basic research to fuel cell in the application of energy field, and the kind of fuel cell and range of application also constantly obtain expanding.Last century the eighties; Microbiological fuel cell is proved and can be applied to daily productive life process; But microbiological fuel cell is difficult to the organic pollution complete oxidation, simultaneously because the influence of the life cycle of microbe own makes microbiological fuel cell lack the long-time stability of operation.
In recent years, TiO
2Be proved to be the semiconductor light-catalyst that a kind of efficient, stable, non-selectivity and material are easy to get.TiO
2Photocatalysis technology almost can make the pollutant permineralization in the sky G&W as a kind of high-level oxidation technology.Find TiO from Fujishima in 1972
2But since the photocatalysis splitting water, TiO
2The conductor photocatalysis technology has obtained extensive studies gradually aspect treatment of organic matters of organic.Because TiO
2The stability of photocatalysis technology with and can overcome the defective that fuel cell exists at present in the advantage aspect the organic pollution processing, therefore with TiO
2Photocatalysis technology is introduced fuel cell system will play facilitation to the expansion of fuel cell applications use.
Retrieval through to prior art is found, Chinese patent document number CN101254961, and Granted publication day 2009-7-8 has put down in writing a kind of " TiO
2Film electrode photoelectric turnplate is handled the method for organic wastewater with difficult degradation thereby ", this technology has comprised a kind of single composite rotating disk photoelectricity liquid film reactor of dynamic light anode: with TiO
2Membrane electrode is made into rotating disk, and half of rotating disk is immersed in the water, and is half the in air, utilizes the rotation of rotating disk to make aerial TiO
2The membrane electrode surface portion has formed tens microns liquid film; Solved the exciting light in the traditional reactor and must just can shine the problem on the electrode through the waste water layer of thicker (several centimetres often); Strengthened the utilance and the mass-transfer efficiency of exciting light simultaneously, thereby can adopt the small-power low pressure mercury lamp to make excitation source, having reduced energy consumption does not need recirculating cooling water system; Simplify device, practiced thrift valuable excitation source.In the reaction tank, the solution of anode region and cathode zone is rapid the mixing owing to the rotation of rotating disk but anode and negative electrode exist together, and the oxidation product that causes the anode region to produce with the reduzate that the cathodic region produces recombination reaction takes place because rotation mixes.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that exists in the prior art, a kind of TiO is provided
2Base optic catalytic combination electrode fuel cell is handled the apparatus and method of organic wastewater
The present invention realizes through following technical scheme.
A kind of TiO
2Base optic catalytic combination electrode fuel-cell device; Comprise speed regulator, CD-ROM drive motor, photocathode rotating shaft, photocathode rotating disk, some light anodes, light anode-supported frame, fuel cell reaction pond and excitation sources; Bottom, said fuel cell reaction pond is provided with a mozzle; Water pump is installed on mozzle, and the delivery port of said mozzle is positioned at the top of said smooth anode.
Said fuel cell reaction pond comprises light anode reaction pond, photocathode reaction tank and amberplex, is connected through amberplex between light anode reaction pond and the photocathode reaction tank, and the water inlet of mozzle is arranged on bottom, light anode reaction pond.
Said smooth anode top is provided with sealing overflow launder or overflow launder.
A kind of TiO that utilizes
2Base optic catalytic combination electrode fuel-cell device is handled the method for organic wastewater, comprises the steps:
The first step is with TiO
2Photochemical catalyst loads on the light anode substrate, and with single chip mode or multi-disc series system the light anode is fixed on the anode-supported frame;
In second step, in the fuel cell reaction pond, add organic wastewater, and the light anode is placed in the light anode reaction pond;
The 3rd step was placed on photocathode in the photocathode reaction tank, and the photocathode rotating shaft is connected with CD-ROM drive motor, and the light anode is connected with photocathode through outer lead;
The 4th step; Switch on the pump; Making organic wastewater from the mozzle of bottom, light anode reaction pond, transfer to the light anode top flows down; Form liquid film at photoanode surface; Start CD-ROM drive motor simultaneously; Rotating speed by speed regulator control photocathode rotating disk makes the photocathode dial rotation, makes cathode surface also form one deck liquid film;
In the 5th step, excitation source irradiates light anode makes exciting light see through liquid film and shines photoanode surface;
The 6th step, sample analysis after processing a period of time, the absorbance of mensuration simulative organic wastewater rhodamine B is asked chroma removal rate (%).
The said processing time is 30-120min.
Said rotating speed is 10-90rpm.
The material of said photocathode rotating disk is Cu, Zn, Fe, Ti, Ag or graphite.
The base material of said smooth anode is titanium, stainless steel, nickel or boron-doped diamond.
Said smooth anode is interlayer light anode or swash plate light anode; Wherein, said interlayer light anode comprises interlayer light anode substrate and shell, and shell is encapsulated in the outside of interlayer light anode substrate; Said cover top portion and bottom are provided with through hole, are provided with the space between shell and the interlayer light anode substrate.
Said smooth anode is a rectangle.
The TiO that the present invention is unique
2Base optic catalytic combination electrode fuel-cell device has the following advantages: TiO
2Photocatalysis technology almost can make the pollutant permineralization in the sky G&W as the high-level oxidation technology that a kind of efficient, stable, non-selectivity and material are easy to get, and can overcome the above-mentioned defective that fuel cell exists.The fuel battery energy of two reaction tank structures effectively stops invalid compound in solution of oxidation product and reduzate, and utilizes metal and N-semiconductor TiO
2Electrical potential difference between Schottky barrier, anode and cathode material that contact forms impels light induced electron to transfer to negative electrode from anode, has reduced light induced electron and hole at TiO
2The recombination losses on surface has improved the utilance of exciting light and the degradation efficiency of pollutant.The rotation stirring action of negative electrode rotating disk helps organic wastewater and O
2Contact, further promoted the degradation rate of organic wastewater.Light induced electron shifts through external circuit simultaneously, has formed stable photoelectric current and correspondent voltage, thereby also can obtain additional electric energy.Adopt the light anode of different structure, improve the treatment effeciency of organic wastewater.The light anode adopts rectangular design, makes current more even at the liquid film that photoanode surface forms, and makes TiO
2The more effective processing organic wastewater of base optic catalytic combination electrode fuel-cell device.
Description of drawings
Fig. 1 monolithic interlayer light anode TiO
2Base optic catalytic combination electrode fuel-cell device sketch map.
Fig. 2 multi-disc interlayer light anode TiO
2Base optic catalytic combination electrode fuel-cell device sketch map.
Fig. 3 monolithic swash plate light anode TiO
2Base optic catalytic combination electrode fuel-cell device sketch map.
Fig. 4 multi-disc swash plate light anode TiO
2Base optic catalytic combination electrode fuel-cell device sketch map.
Fig. 5 monolithic rotating disk light anode TiO
2Base optic catalytic combination electrode fuel-cell device sketch map.
Fig. 6 multi-disc rotating disk light anode TiO
2Base optic catalytic combination electrode fuel-cell device sketch map.
Among the figure, 1 is speed regulator, and 2 is motor, and 3 is the photocathode rotating shaft, and 31 is metal rotating shaft; 4 is the photocathode rotating disk, and 51 is interlayer light anode, and 52 is swash plate light anode, and 53 is rotating disk light anode, and 6 are the sealing overflow launder; 61 is overflow launder, and 62 is the polymethyl methacrylate rotating shaft, and 7 are the cathode reaction pond, and 8 is amberplex, and 9 is the anode reaction pond; 10 is outer lead, and 11 is galvo-recorder, and 12 is the voltage recorder, and 13 is excitation source, and 14 is aluminium foil; 15 is light anode-supported frame, and 16 is carbon brush, and 17 is water pump, and 18 is the polymethyl methacrylate rotating shaft.
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment is implemented under with technical scheme prerequisite of the present invention, provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Following examples are TiO
2The embodiment of base optic catalytic combination electrode fuel-cell device.
Embodiment 1
The TiO of monolithic interlayer light anode
2The structure of base optic catalytic combination electrode fuel-cell device.
A kind of TiO of monolithic interlayer light anode
2Base optic catalytic combination electrode fuel-cell device; Comprise speed regulator 1, CD-ROM drive motor 2, photocathode rotating shaft 3; Photocathode rotating disk 4, interlayer light anode 51, sealing overflow launder 6 and light anode-supported frame 15; Fuel cell reaction pond and excitation source; Wherein the fuel cell reaction pond comprises light anode reaction pond 9, photocathode reaction tank 7 and amberplex 8, is connected through amberplex 8 between light anode reaction pond 9 and the photocathode reaction tank 7, and this amberplex is cation-exchange membrane or cluster ion exchange membrane.Interlayer light anode 51 comprises interlayer light anode substrate and envelope of quartz glass; Interlayer light anode substrate is a rectangle; Its material is titanium, stainless steel, nickel or boron-doped diamond, utilizes sol-gel process, direct heat oxidizing process or anode oxidation method load TiO on the interlayer light anode substrate
2Photochemical catalyst, and encapsulate with envelope of quartz glass in the outside of interlayer light anode substrate, envelope of quartz glass top and bottom are provided with through hole, are provided with the space between interlayer light anode substrate and the shell, make organic wastewater in the light anode reaction pond from TiO
2Flow through in the interlayer between film and the quartz glass.Interlayer light anode 51 is fixedly mounted on the light anode-supported frame 15, and light anode-supported frame 15 is provided with carbon brush 16.The material of photocathode rotating disk 4 is Cu, Zn, Fe, Ti, Ag or graphite, and photocathode rotating disk 4 is fixedly mounted in the photocathode rotating shaft 3, and photocathode rotating shaft 3 is provided with carbon brush 16.Photocathode rotating disk 4 relies on carbon brush 16 to be connected through the carbon brush 16 of outer lead 10 with interlayer light anode 51 places.Galvo-recorder 11 and voltage recorder 12 are installed on the outer lead.Side near interlayer light anode 51 is provided with excitation source 13, and this excitation source is a uviol lamp, in the arranged outside of excitation source aluminium foil 14 is arranged.The bottom in light anode reaction pond 9 is provided with a circulation mozzle; The delivery port of mozzle is positioned at the top of said smooth anode; Organic wastewater in the light anode reaction pond is transferred in the sealing overflow launder 6 of interlayer light anode top through water pump 17; Sealing overflow launder 6 is connected with the through hole at quartz glass top, and organic wastewater is from sealing overflow launder 6 and flow through interlayer light anode and at the TiO of interlayer light anode substrate
2Photocatalyst surface forms liquid film.
Speed regulator 1 is connected with CD-ROM drive motor 2, and CD-ROM drive motor 2 is connected with photocathode rotating shaft 3, fixed installation photocathode rotating disk 4 in the photocathode rotating shaft 3, fixed installation interlayer light anode 51 on the light anode-supported frame 15.Start CD-ROM drive motor 2; Drive photocathode rotating shaft 3 rotations; Photocathode rotating disk 4 is rotated thereupon; Switch on the pump 17 simultaneously, the organic wastewater in the light anode reaction pond is transferred in the sealing overflow launder 6 of interlayer light anode top, flow through interlayer light anode and at the TiO of interlayer light anode substrate from sealing overflow launder 6 again
2Photocatalyst surface forms liquid film.Speed through 4 rotations of controller 1 control photocathode rotating disk.Circular flow through organic wastewater in the water pump 17 control light anode reaction ponds.The excitation light irradiation that excitation source 13 sends is on interlayer light anode 51 surfaces, and aluminium foil 14 can be used for raising and excites light intensity.
The TiO of multi-disc series connection interlayer light anode
2The structure of base optic catalytic combination electrode fuel-cell device.
A kind of TiO of multi-disc series connection interlayer light anode
2Base optic catalytic combination electrode fuel-cell device; Comprise speed regulator 1, CD-ROM drive motor 2, photocathode rotating shaft 3; Photocathode rotating disk 4, multi-disc series connection interlayer light anode 51, sealing overflow launder 6; Fuel cell reaction pond and excitation source; Wherein the fuel cell reaction pond comprises light anode reaction pond 9, photocathode reaction tank 7 and amberplex 8, is connected through amberplex 8 between light anode reaction pond 9 and the photocathode reaction tank 7, and this amberplex is cation-exchange membrane or cluster ion exchange membrane.Interlayer light anode 51 comprises interlayer light anode substrate and shell; Shell is a quartz glass; Interlayer light anode is a rectangle, and its base material is titanium, stainless steel, nickel or boron-doped diamond, utilizes sol-gel process, direct heat oxidizing process or anode oxidation method load TiO on the interlayer light anode substrate
2Photochemical catalyst, and encapsulate with envelope of quartz glass in the outside of interlayer light anode substrate, envelope of quartz glass top and bottom are provided with through hole, are provided with the space between interlayer light anode substrate and the shell, make organic wastewater in the light anode reaction pond from TiO
2Flow through in the interlayer between film and the quartz glass.Photocathode rotating disk 4 materials are Cu, Zn, Fe, Ti, Ag or graphite, and photocathode rotating disk 4 is fixedly mounted on photocathode rotating shaft 3, and photocathode rotating shaft 3 is provided with carbon brush 16, multi-disc series connection interlayer light anode 51 coaxial being fixedly mounted on the light anode-supported frame 15.Photocathode rotating disk 4 relies on carbon brush 16 to be connected with the carbon brush 16 that is in outermost a slice interlayer light anode 51 places through outer lead 10.Galvo-recorder 11 and voltage recorder 12 are installed on the outer lead.Be provided with excitation source 13 between the interlayer light anode 51 in twos, this excitation source is a uviol lamp, in the arranged outside of the excitation source that is in both sides aluminium foil 14 is arranged.The bottom in light anode reaction pond 9 is provided with a circulation mozzle; The delivery port of mozzle is positioned at the top of said smooth anode; Organic wastewater in the light anode reaction pond is transferred in the sealing overflow launder 6 of multi-disc interlayer light anode top through water pump 17; Sealing overflow launder 6 is connected with the through hole at quartz glass top, and organic wastewater is from sealing overflow launder 6 and flow through multi-disc interlayer light anode and at the TiO of interlayer light anode substrate
2Photocatalyst surface forms liquid film.
Speed regulator 1 is connected with CD-ROM drive motor 2, and CD-ROM drive motor 2 is connected with photocathode rotating shaft 3, fixed installation photocathode rotating disk 4 in the photocathode rotating shaft 3, and multi-disc interlayer light anode 51 is installed in series on the light anode-supported frame 15.Start CD-ROM drive motor 2; Drive photocathode rotating shaft 3 rotations; Photocathode rotating disk 4 is rotated thereupon; Switch on the pump 17 simultaneously, make organic wastewater in the light anode reaction pond transfer to the sealing overflow launder 6 of multi-disc interlayer light anode top, flow through multi-disc interlayer light anode and at the TiO of interlayer light anode substrate from sealing overflow launder 6 again
2Photocatalyst surface forms liquid film.Speed through 4 rotations of controller 1 control photocathode rotating disk.Circular flow through organic wastewater in the water pump 17 control light anode reaction ponds.The excitation light irradiation that excitation source 13 sends is on interlayer light anode 51 surfaces, and aluminium foil 14 can be used for raising and excites light intensity.
The TiO of monolithic swash plate light anode
2The structure of base optic catalytic combination electrode fuel-cell device.
A kind of TiO of monolithic swash plate light anode
2Base optic catalytic combination electrode fuel-cell device comprises speed regulator 1, CD-ROM drive motor 2, photocathode rotating shaft 3, photocathode rotating disk 4; Swash plate light anode 52; Water pump 17, fuel cell reaction pond and excitation source, wherein the fuel cell reaction pond comprises light anode reaction pond 9, photocathode reaction tank 7 and amberplex 8; Be connected through amberplex 8 between light anode reaction pond 9 and the photocathode reaction tank 7, this amberplex is cation-exchange membrane or cluster ion exchange membrane.The substrate of swash plate light anode 52 is a rectangle, and base material is titanium, stainless steel, nickel or boron-doped diamond, and the material of photocathode rotating disk 4 is Cu, Zn, Fe, Ti, Ag or graphite.Utilize sol-gel process, direct heat oxidizing process or anode oxidation method load TiO in 52 substrates of swash plate light anode
2 Photocathode rotating disk 4 is fixedly mounted in the photocathode rotating shaft 3, and photocathode rotating shaft 3 is provided with carbon brush 16.Swash plate light anode 52 is fixedly mounted on the light anode-supported frame 15, and light anode-supported frame 15 is provided with carbon brush 16.Photocathode rotating disk 4 relies on carbon brush 16 to be connected through the carbon brush 16 of outer lead 10 with swash plate light anode 52 places.Galvo-recorder 11 and voltage recorder 12 are installed on the outer lead.Side near swash plate light anode 52 is provided with excitation source 13, and this excitation source is a uviol lamp, in the arranged outside of excitation source aluminium foil 14 is arranged.The bottom in light anode reaction pond 9 is provided with a circulation mozzle; The delivery port of mozzle is positioned at the top of said smooth anode; Organic wastewater in the light anode reaction pond is transferred in the overflow launder 61 of swash plate light anode top through water pump 17, flow through swash plate light anode and at the TiO of swash plate light anode substrate from overflow launder 61 again
2Photocatalyst surface forms liquid film.
Speed regulator 1 is connected with CD-ROM drive motor 2, and CD-ROM drive motor 2 is connected with photocathode rotating shaft 3, fixed installation photocathode rotating disk 4 in the photocathode rotating shaft 3, fixed installation swash plate light anode 52 on the light anode-supported frame 15.Start CD-ROM drive motor 2; Drive photocathode rotating shaft 3 rotations, photocathode rotating disk 4 is rotated thereupon, switch on the pump 17 simultaneously; Make organic wastewater in the light anode reaction pond transfer to the overflow launder 61 of swash plate light anode top, flow through swash plate light anode and at the TiO of swash plate light anode substrate from overflow launder 61 again
2Photocatalyst surface forms liquid film.Speed through 4 rotations of speed regulator 1 control photocathode rotating disk.Circular flow through organic wastewater in the water pump 17 control light anode reaction ponds.The excitation light irradiation that excitation source 13 sends is on swash plate light anode 52 surfaces, and aluminium foil 14 can be used for raising and excites light intensity.
The TiO of multi-disc series connection swash plate light anode
2The structure of base optic catalytic combination electrode fuel-cell device.
A kind of TiO of multi-disc series connection swash plate light anode
2Base optic catalytic combination electrode fuel-cell device comprises speed regulator 1, CD-ROM drive motor 2, photocathode rotating shaft 3, photocathode rotating disk 4; Multi-disc series connection swash plate light anode 52; Water pump 17, fuel cell reaction pond and excitation source, wherein the fuel cell reaction pond comprises light anode reaction pond 9, photocathode reaction tank 7 and amberplex 8; Be connected through amberplex 8 between light anode reaction pond 9 and the photocathode reaction tank 7, this amberplex is cation-exchange membrane or cluster ion exchange membrane.The substrate of swash plate light anode 52 is a rectangle, and base material is titanium, stainless steel, nickel or boron-doped diamond, and photocathode rotating disk 4 materials are Cu, Zn, Fe, Ti, Ag or graphite.Utilize sol-gel process, direct heat oxidizing process or anode oxidation method load TiO in 52 substrates of swash plate light anode
2 Photocathode rotating disk 4 is fixedly mounted on photocathode rotating shaft 3, and photocathode rotating shaft 3 is provided with carbon brush 16, multi-disc series connection swash plate light anode 52 coaxial being fixedly mounted on the light anode-supported frame 15.Photocathode rotating disk 4 relies on carbon brush 16 to be connected with the carbon brush 16 that is in outermost a slice swash plate light anode 52 places through outer lead 10.Galvo-recorder 11 and voltage recorder 12 are installed on the outer lead.Be provided with excitation source 13 between the swash plate light anode 52 in twos, this excitation source is a uviol lamp, in the arranged outside of the excitation source that is in both sides aluminium foil 14 is arranged.The bottom in light anode reaction pond 9 is provided with a circulation mozzle; The delivery port of mozzle is positioned at the top of said smooth anode; Organic wastewater in the light anode reaction pond is transferred in the overflow launder 61 of multi-disc swash plate light anode top through water pump 17, flow through multi-disc swash plate light anode and at the TiO of swash plate light anode substrate from overflow launder 61 again
2Photocatalyst surface forms liquid film.
Speed regulator 1 is connected with CD-ROM drive motor 2, and CD-ROM drive motor 2 is connected with photocathode rotating shaft 3, fixed installation photocathode rotating disk 4 in the photocathode rotating shaft 3, and multi-disc swash plate light anode 52 is installed in series on the light anode-supported frame 15.Start CD-ROM drive motor 2; Drive photocathode rotating shaft 3 rotations; Photocathode rotating disk 4 is rotated thereupon; Switch on the pump 17 simultaneously, make organic wastewater in the light anode reaction pond transfer to the overflow launder 61 of multi-disc swash plate light anode top, flow through multi-disc swash plate light anode and at the TiO of swash plate light anode substrate from overflow launder 61 again
2Photocatalyst surface forms liquid film.Speed through 4 rotations of speed regulator 1 control photocathode rotating disk.Circular flow through organic wastewater in the water pump 17 control light anode reaction ponds.The excitation light irradiation that excitation source 13 sends is on swash plate light anode 52 surfaces, and aluminium foil 14 can be used for raising and excites light intensity.
Embodiment 5
The TiO of monolithic rotating disk light anode
2The structure of base optic catalytic combination electrode fuel-cell device.
A kind of TiO of monolithic rotating disk light anode
2Base optic catalytic combination electrode fuel-cell device comprises speed regulator 1, CD-ROM drive motor 2, metal rotating shaft 31, photocathode rotating disk 4; Light anode rotating disk 53; Polymethyl methacrylate rotating shaft 18, fuel cell reaction pond and excitation source, wherein the fuel cell reaction pond comprises light anode reaction pond 9, photocathode reaction tank 7 and amberplex 8; Be connected through amberplex 8 between light anode reaction pond 9 and the photocathode reaction tank 7, this amberplex is cation-exchange membrane or cluster ion exchange membrane.The base material of light anode rotating disk 53 is titanium, stainless steel, nickel or boron-doped diamond, and photocathode rotating disk 4 materials are Cu, Zn, Fe, Ti, Ag or graphite.Utilize sol-gel process, direct heat oxidizing process or anode oxidation method load TiO in 53 substrates of light anode rotating disk
2 Photocathode rotating disk 4 and light anode rotating disk 53 coaxial being fixedly mounted on the metal rotating shaft 31 are provided with carbon brush 16 on its metal rotating shaft, use polymethyl methacrylate rotating shaft 18 to connect the metal rotating shaft 31 of anode and negative electrode.Photocathode rotating disk 4 relies on carbon brush 16 to be connected through the carbon brush 16 of outer lead 10 with light anode rotating disk 53 places.Galvo-recorder 11 and voltage recorder 12 are installed on the outer lead.Side near light anode rotating disk 53 is provided with excitation source 13, and this excitation source is a uviol lamp, in the arranged outside of excitation source aluminium foil 14 is arranged.
Speed regulator 1 is connected with CD-ROM drive motor 2, and CD-ROM drive motor 2 is connected with metal rotating shaft 31, and coaxial fixed installation photocathode rotating disk 4 and light anode rotating disk 53 on the metal rotating shaft 31 use polymethyl methacrylate rotating shaft 18 to connect anode and negative electrode metal rotating shaft 31 separately.Start CD-ROM drive motor 2, drive metal rotating shaft 31 and rotate, photocathode rotating disk 4 and light anode rotating disk 53 are rotated thereupon, and control the speed of photocathode rotating disk 4 and 53 rotations of light anode rotating disk through controller 1.The excitation light irradiation that excitation source 13 sends is on light anode rotating disk 53 surfaces, and aluminium foil 14 can be used for raising and excites light intensity.
Embodiment 6
The TiO of multi-disc series connection rotating disk light anode
2The structure of base optic catalytic combination electrode fuel-cell device.
A kind of TiO of multi-disc series connection rotating disk light anode
2Base optic catalytic combination electrode fuel-cell device comprises speed regulator 1, CD-ROM drive motor 2, metal rotating shaft 31, photocathode rotating disk 4; Light anode rotating disk 53; Polymethyl methacrylate rotating shaft 18, fuel cell reaction pond and excitation source, wherein the fuel cell reaction pond comprises light anode reaction pond 9, photocathode reaction tank 7 and amberplex 8; Be connected through amberplex 8 between light anode reaction pond 9 and the photocathode reaction tank 7, this amberplex is cation-exchange membrane or cluster ion exchange membrane.The base material of light anode rotating disk 53 is titanium, stainless steel, nickel or boron-doped diamond, and photocathode rotating disk 4 materials are Cu, Zn, Fe, Ti, Ag or graphite.Utilize sol-gel process, direct heat oxidizing process or anode oxidation method load TiO in 53 substrates of light anode rotating disk
2 Photocathode rotating disk 4 is fixedly mounted on metal rotating shaft 31; Metal rotating shaft 31 is provided with carbon brush 16; Coaxial being fixedly mounted on the metal rotating shaft 31 of multi-disc light anode rotating disk 53 series connection; Each sheet light anode rotating disk 53 is connected through carbon brush 16 at metal rotating shaft 31 places between any two or links to each other through lead, uses polymethyl methacrylate rotating shaft 18 to connect anode and negative electrode metal rotating shaft 31 separately.Photocathode rotating disk 4 relies on carbon brush 16 to be connected with the carbon brush 16 that is in outermost a slice light anode rotating disk 53 places through outer lead 10.Galvo-recorder 11 and voltage recorder 12 are installed on the outer lead.Be provided with excitation source 13 between the light anode rotating disk 53 in twos, this excitation source is a uviol lamp, in the arranged outside of the excitation source that is in both sides aluminium foil 14 is arranged.
Speed regulator 1 is connected with CD-ROM drive motor 2, and CD-ROM drive motor 2 is connected with metal rotating shaft 31, and coaxial fixed installation photocathode rotating disk 4 and multi-disc light anode rotating disk 53 on the metal rotating shaft 31 use polymethyl methacrylate rotating shaft 18 to connect anode and negative electrode metal rotating shaft 31 separately.Start CD-ROM drive motor 2, drive metal rotating shaft 31 and rotate, photocathode rotating disk 4 and multi-disc light anode rotating disk 53 are rotated thereupon, and control the speed of photocathode rotating disk 4 and 53 rotations of multi-disc light anode rotating disk through speed regulator 1.The excitation light irradiation that excitation source 13 sends is on light anode rotating disk 53 surfaces, and aluminium foil 14 can be used for raising and excites light intensity.
Following examples are for utilizing TiO
2Base optic catalytic combination electrode fuel-cell device is handled the embodiment of the method for organic wastewater, adopts the TiO of monolithic interlayer light anode or monolithic swash plate light anode
2Base optic catalytic combination electrode fuel-cell device.
Embodiment 7
The TiO of different anode substrate
2Base optic catalytic combination electrode fuel-cell device is handled the method for organic wastewater.
Like Fig. 1,3, shown in 5, process object is 25mg/L rhodamine B (pH2.5,2.0g/LNa
2SO
4) simulative organic wastewater.Wastewater volume is 200ml.
1) adopting the titanium plate is the light anode substrate, utilizes sol-gel process with TiO
2Photochemical catalyst loads on the light anode substrate, and with single chip mode the light anode is fixed on the anode-supported frame.
2) in the fuel cell reaction pond, add rhodamine B, the light anode is placed in the light anode reaction pond, the anode-supported frame is near the position of the water surface in light anode reaction pond, and half is immersed in the organic wastewater to make the light anode.
3) make photocathode with the copper coin dish; Be placed in the photocathode reaction tank, the photocathode rotating shaft is near the water surface site of photocathode reaction tank, and half that makes photocathode is immersed in the organic wastewater; The photocathode rotating shaft is connected with CD-ROM drive motor, and the light anode is connected with photocathode through outer lead.
4) switch on the pump; Make organic wastewater from the mozzle of bottom, light anode reaction pond, transfer to the light anode top; And flow down from the light anode top, form liquid film at photoanode surface, start CD-ROM drive motor simultaneously; Rotating speed through speed regulator control cathode rotating disk is 70rpm, makes cathode surface also form one deck liquid film; Start the CD-ROM drive motor of rotating disk fuel cell, and be 70rpm, make anode and cathode surface formation one deck liquid film through the rotating speed of speed regulator control anode and negative electrode rotating disk.
5) adopt the 11W254nm low pressure mercury lamp as excitation source, the irradiation anode makes exciting light see through liquid film and shines anode surface.
6) sample analysis behind the processing time 2h is measured the absorbance of rhodamine B at the 563nm place, asks chroma removal rate (%).
The result that each anode substrate material of the present invention and traditional titanium plate light anode are measured contrasts as follows:
Can find out two kinds of dissimilar TiO from above result
2The photocatalysis fuel cell all has rhodamine B when using different base light anode removes efficient preferably.
The TiO of different system film modes
2Base optic catalytic combination electrode fuel-cell device is handled the method for organic wastewater.
In embodiment 8, the substrate of light anode is a titanium plate light anode, utilizes diverse ways with TiO
2Photochemical catalyst loads in the substrate, measures the absorbance of rhodamine B at the 563nm place, asks chroma removal rate (%), measures the current average of external circuit 2h simultaneously, and its result is following:
Can find out two kinds of dissimilar TiO from above result
2The photocatalysis fuel cell all has chromaticity removing effect preferably when using different system film modes, just because the difference of production method makes the result slightly variant.
The TiO of different cathode materials
2Base optic catalytic combination electrode fuel-cell device is handled the method for organic wastewater.
In embodiment 9, the substrate of light anode is a titanium plate light anode, adopts different photocathode materials, measures the absorbance of rhodamine B at the 563nm place, asks chroma removal rate (%), and its result is following:
As can be seen from the above results, different photocathode materials has tangible influence to the clearance of colourity, wherein, adopts the best results of Cu as photocathode material.
The TiO of different rotating speeds
2Base optic catalytic combination electrode fuel-cell device is handled the method for organic wastewater.
In embodiment 10, the substrate of light anode is a titanium plate light anode, selects different negative electrode rotary speeds, measures the absorbance of rhodamine B at the 563nm place, asks chroma removal rate (%), and its result is following:
Can find out that from above result the raising of negative electrode rotating speed helps the raising of cathode reaction pond treatment effect, but because the circulation rate of anode organic wastewater is relatively independent, so the influence of negative electrode change in rotational speed antianode reaction tank treatment effect is smaller.
The TiO of different disposal time
2Base optic catalytic combination electrode fuel-cell device is handled the method for organic wastewater.
In embodiment 10, the substrate of light anode is a titanium plate light anode, adopts the different processing times, measures the absorbance of rhodamine B at the 563nm place, asks chroma removal rate (%), and the result is following:
As can be seen from the above results, the proper extension processing time helps the raising of treatment effect.
TiO2 base optic catalytic combination electrode fuel-cell device is handled variable concentrations organic wastewater.
In embodiment 12, the substrate of light anode is a titanium plate light anode, adopts the organic wastewater of variable concentrations, measures the absorbance of rhodamine B at the 563nm place, asks chroma removal rate (%), and the result is following:
Can find out that from above result swash plate photocatalysis fuel cell has certain advantage when treatment of high concentration waste water.
TiO
2The situation of change of voltage and current in the base optic catalytic combination electrode fuel-cell device processing procedure.
Like Fig. 1,3, shown in 5, process object is 25mg/L rhodamine B (pH2.5,2.0g/LNa
2SO
4) simulative organic wastewater.Wastewater volume is 200ml.
1) adopting the titanium plate is substrate, utilizes sol-gel process with TiO
2Photochemical catalyst loads in the substrate, and with single chip mode the light anode is fixed on the anode-supported frame.
2) the light anode is placed in the reaction tank, the anode-supported frame is near the position of the water surface in light anode reaction pond, and half is immersed in the organic wastewater to make the light anode.
3) make photocathode with the copper coin dish; Be placed in the photocathode reaction tank, the photocathode rotating shaft is near the water surface site of photocathode reaction tank, and half that makes photocathode is immersed in the organic wastewater; The photocathode rotating shaft is connected with CD-ROM drive motor, and the light anode is connected with photocathode through outer lead.
4) switch on the pump; Make organic wastewater from the mozzle of bottom, light anode reaction pond, transfer to the light anode top; And flow down from the light anode top, form liquid film at photoanode surface, start CD-ROM drive motor simultaneously; Rotating speed through speed regulator control cathode rotating disk is 70rpm, makes cathode surface also form one deck liquid film; Start the CD-ROM drive motor of rotating disk fuel cell, and be 70rpm, make anode and cathode surface formation one deck liquid film through the rotating speed of speed regulator control anode and negative electrode rotating disk.
5) adopt the 11W254nm low pressure mercury lamp as excitation source, the irradiation anode makes exciting light see through liquid film and shines anode surface.
6) sample analysis behind the processing time 2h is measured the absorbance of rhodamine B at the 563nm place, asks the situation of change of voltage and current.
Can find out that from above result different fuel cell structures has to a certain degree influence to running parameters such as voltage that fuel cell system produced, electric currents.
More specifically, the light anode can adopt interlayer light anode and swash plate light anode.When adopting interlayer light anode; Switch on the pump; Make organic wastewater from the mozzle of bottom, light anode reaction pond, transfer to the sealing overflow launder 6 of interlayer light anode top; Sealing overflow launder 6 is connected with the through hole at quartz glass top, and organic wastewater is from sealing overflow launder 6 and flow through interlayer light anode and at the TiO of interlayer light anode substrate
2Photocatalyst surface forms liquid film; When adopting swash plate light anode, switch on the pump, make organic wastewater from the mozzle of bottom, light anode reaction pond, transfer to the overflow launder 61 of interlayer light anode top, flow through swash plate light anode and at the TiO of interlayer light anode substrate from overflow launder 61 again
2Photocatalyst surface forms liquid film.
The foregoing description presentation of results, TiO of the present invention
2Base optic catalytic combination electrode fuel-cell device utilizes TiO
2Photocatalysis technology almost can make the pollutant permineralization in the water, and TiO
2Semi-conducting material as a kind of efficient, stable, environmental protection and non-selectivity can overcome the defective that fuel cell exists at present.The structure of two reaction tanks can effectively stop invalid compound in solution of oxidation product and reduzate, utilizes metal and N-semiconductor TiO simultaneously
2Electrical potential difference between Schottky barrier, anode and cathode material that contact forms impels light induced electron to transfer to negative electrode from anode, has reduced light induced electron and hole at TiO
2The recombination losses on surface has improved the utilance of exciting light and the degradation efficiency of pollutant.The rotation stirring action of negative electrode rotating disk helps organic wastewater and O
2Contact, further promoted the degradation rate of organic wastewater.Light induced electron shifts through external circuit simultaneously, has formed stable photoelectric current and correspondent voltage, thereby also can obtain additional electric energy.Adopt the TiO of interlayer light anode
2Base optic catalytic combination electrode fuel-cell device, current can be at TiO from interlayer intermediate flow mistake
2Photocatalytic surfaces forms thin liquid film, can make TiO
2Photocatalysis produces effect better.Adopt the TiO of swash plate light anode
2Base optic catalytic combination electrode fuel-cell device, the liquid film of its generation is thinner, and UV Absorption is lost still less, can further improve the treatment effeciency of organic wastewater.The light anode adopts rectangular design, makes current more even at the liquid film that photoanode surface forms, and makes TiO
2The more effective processing organic wastewater of base optic catalytic combination electrode fuel-cell device.
Claims (10)
1. TiO
2Base optic catalytic combination electrode fuel-cell device; Comprise speed regulator, CD-ROM drive motor, photocathode rotating shaft, photocathode rotating disk, some light anodes, light anode-supported frame, fuel cell reaction pond and excitation sources; It is characterized in that; Bottom, said fuel cell reaction pond is provided with a mozzle, and water pump is installed on mozzle, and the delivery port of said mozzle is positioned at the top of said smooth anode.
2. TiO according to claim 1
2Base optic catalytic combination electrode fuel-cell device; It is characterized in that; Said fuel cell reaction pond comprises light anode reaction pond, photocathode reaction tank and amberplex; Be connected through amberplex between light anode reaction pond and the photocathode reaction tank, the water inlet of mozzle is arranged on bottom, light anode reaction pond.
3. TiO according to claim 1
2Base optic catalytic combination electrode fuel-cell device is characterized in that, said smooth anode top is provided with sealing overflow launder or overflow launder.
4. one kind is utilized TiO as claimed in claim 1
2Base optic catalytic combination electrode fuel-cell device is handled the method for organic wastewater, it is characterized in that, comprises the steps:
The first step is with TiO
2Photochemical catalyst loads on the light anode substrate, and with single chip mode or multi-disc series system the light anode is fixed on the anode-supported frame;
In second step, in the fuel cell reaction pond, add organic wastewater, and the light anode is placed in the light anode reaction pond;
The 3rd step was placed on photocathode in the photocathode reaction tank, and the photocathode rotating shaft is connected with CD-ROM drive motor, and the light anode is connected with photocathode through outer lead;
The 4th step; Switch on the pump; Making organic wastewater from the mozzle of bottom, light anode reaction pond, transfer to the light anode top flows down; Form liquid film at photoanode surface; Start CD-ROM drive motor simultaneously; Rotating speed by speed regulator control photocathode rotating disk makes the photocathode dial rotation, makes cathode surface also form one deck liquid film;
In the 5th step, excitation source irradiates light anode makes exciting light see through liquid film and shines photoanode surface;
The 6th step, sample analysis after processing a period of time, the absorbance of mensuration rhodamine B is asked chroma removal rate (%).
5. TiO according to claim 4
2Base optic catalytic combination electrode fuel-cell device is handled the method for organic wastewater, it is characterized in that the said processing time is 30-120min.
6. TiO according to claim 4
2Base optic catalytic combination electrode fuel-cell device is handled the method for organic wastewater, it is characterized in that said rotating speed is 10-90rpm.
7. according to claim 1 or 4 described TiO
2The method of base optic catalytic combination electrode fuel-cell device/processing organic wastewater is characterized in that, the material of said photocathode rotating disk is Cu, Zn, Fe, Ti, Ag or graphite.
8. according to claim 1 or 4 described TiO
2The method of base optic catalytic combination electrode fuel-cell device/processing organic wastewater is characterized in that, the base material of said smooth anode is titanium, stainless steel, nickel or boron-doped diamond.
9. according to claim 1 or 4 described TiO
2The method of base optic catalytic combination electrode fuel-cell device/processing organic wastewater; It is characterized in that said smooth anode is interlayer light anode or swash plate light anode, wherein; Said interlayer light anode comprises interlayer light anode substrate and shell; Shell is encapsulated in the outside of interlayer light anode substrate, and said cover top portion and bottom are provided with through hole, is provided with the space between shell and the interlayer light anode substrate.
10. according to claim 1 or 4 described TiO
2The method of base optic catalytic combination electrode fuel-cell device/processing organic wastewater is characterized in that, said smooth anode is a rectangle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110273376.6A CN102403523B (en) | 2011-09-15 | 2011-09-15 | Apparatus and method for processing organic wastewater by using TiO2-based photocatalytic composite-electrode fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110273376.6A CN102403523B (en) | 2011-09-15 | 2011-09-15 | Apparatus and method for processing organic wastewater by using TiO2-based photocatalytic composite-electrode fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102403523A true CN102403523A (en) | 2012-04-04 |
| CN102403523B CN102403523B (en) | 2014-12-10 |
Family
ID=45885493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110273376.6A Active CN102403523B (en) | 2011-09-15 | 2011-09-15 | Apparatus and method for processing organic wastewater by using TiO2-based photocatalytic composite-electrode fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102403523B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261510A (en) * | 2014-08-26 | 2015-01-07 | 江苏恒智纳米科技有限公司 | Photocatalytic device for deeply processing organic wastewater |
| CN104846394A (en) * | 2015-04-15 | 2015-08-19 | 上海交通大学 | Photochemical battery device for co-production of hydrogen and electricity by using high-chroma alcohol-containing wastewater |
| WO2016065882A1 (en) * | 2014-10-30 | 2016-05-06 | 林志勋 | Portable sewage purification and electricity generation apparatus |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353186A (en) * | 2008-09-18 | 2009-01-28 | 上海交通大学 | Double turntable light-sensitive cell liquid membrane reactor photocatalysis organic wastewater processing method |
-
2011
- 2011-09-15 CN CN201110273376.6A patent/CN102403523B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353186A (en) * | 2008-09-18 | 2009-01-28 | 上海交通大学 | Double turntable light-sensitive cell liquid membrane reactor photocatalysis organic wastewater processing method |
Non-Patent Citations (2)
| Title |
|---|
| 刁增辉: "光电化学协同催化降解染料废水的研究", 《中国优秀硕士论文全文数据库 ，工程科技I辑（月刊）》, no. 10, 31 October 2010 (2010-10-31) * |
| 徐云兰: "光电液膜反应器处理染料废水的研究", 《中国博士学位论文全文数据库，工程科技I辑（月刊）》, no. 01, 31 January 2011 (2011-01-31) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261510A (en) * | 2014-08-26 | 2015-01-07 | 江苏恒智纳米科技有限公司 | Photocatalytic device for deeply processing organic wastewater |
| CN104261510B (en) * | 2014-08-26 | 2016-08-24 | 江苏恒智纳米科技有限公司 | The photocatalysis apparatus of deep-treating organic waste water |
| WO2016065882A1 (en) * | 2014-10-30 | 2016-05-06 | 林志勋 | Portable sewage purification and electricity generation apparatus |
| CN104846394A (en) * | 2015-04-15 | 2015-08-19 | 上海交通大学 | Photochemical battery device for co-production of hydrogen and electricity by using high-chroma alcohol-containing wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102403523B (en) | 2014-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100509638C (en) | Method for treating refractory organic wastewater by TiO2 film electrode photoelectric turnplate | |
| Meng et al. | Synergetic photoelectrocatalytic reactors for environmental remediation: a review | |
| Safdar et al. | Microfluidic fuel cells for energy generation | |
| CN101353186B (en) | Processing method for double turntable light-sensitive cell liquid membrane reactor photocatalysis organic wastewater | |
| CN102398955A (en) | Device and method for treating organic wastewater with TiO2 photocatalysis rotary disc fuel cell | |
| CN102603037A (en) | Sunlight-assisted electro-catalysis organic wastewater treatment membrane reactor | |
| CN107162118A (en) | A kind of built-in ceramic micro filter membrane reactor of anode and cathode suitable for source water pollutant removal | |
| Nareejun et al. | Novel photoelectrocatalytic/solar cell improvement for organic dye degradation based on simple dip coating WO3/BiVO4 photoanode electrode | |
| CN101486499B (en) | Apparatus for photoelectric catalytic oxidation of subaqueous organics by solar energy | |
| CN104630816B (en) | Hydrogen production device and technology via photoelectric degradation of organic pollutant based on solar energy and sea water cell collaborative drive | |
| CN1598075A (en) | Titanium dioxide nano tube electrode and its preparation process and application | |
| CN106684508A (en) | Tiled type bipolar optical response photoelectric chemical battery, building roof domestic sewage treatment power generation system and working method | |
| CN109160575A (en) | A kind of double optoelectronic pole systems of automatic bias and application | |
| CN106986482A (en) | A kind of photoelectrochemical degradation waste plant | |
| CN102403523B (en) | Apparatus and method for processing organic wastewater by using TiO2-based photocatalytic composite-electrode fuel cell | |
| CN113060803A (en) | System and method for treating trace estrogen in reclaimed water through electrocatalysis | |
| CN105293644B (en) | Optical electro-chemistry electrolysis installation and the battery lead plate for the optical electro-chemistry electrolysis installation | |
| CN102258971B (en) | Tubular nano titanium dioxide pipe array photocatalysis reactor and preparation method | |
| CN104803444B (en) | Advanced oxidation pollution control technology and device | |
| CN101993129B (en) | Method for treating photoelectrocatalysis of organic wastewater through sharply-structured light anode and photoelectricity rotary disc | |
| EP3990395A1 (en) | Modular photocatalytic system | |
| CN102826631B (en) | Hydrodynamic impeller disk reactor for efficiently evaluating efficiency of photoelectric catalytic reaction | |
| CN101905142A (en) | Titanium dioxide nanotube array electrode photoelectron-catalysis film reactor and application thereof | |
| CN113488663B (en) | Photocatalytic fuel cell with three-dimensional permeable photoanode | |
| CN101774661B (en) | Composite rotating disk liquid film reactor and method for processing organic wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |