CN212246341U - Modularized high-efficiency electrocatalytic oxidation reactor - Google Patents
Modularized high-efficiency electrocatalytic oxidation reactor Download PDFInfo
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- CN212246341U CN212246341U CN202020756756.XU CN202020756756U CN212246341U CN 212246341 U CN212246341 U CN 212246341U CN 202020756756 U CN202020756756 U CN 202020756756U CN 212246341 U CN212246341 U CN 212246341U
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Abstract
The utility model provides a high-efficient electrocatalytic oxidation reactor of modularization. The modular high-efficiency electrocatalytic oxidation reactor comprises a shell; a base disposed at a bottom side of the housing; the reaction bin is arranged in the shell; the water inlet is arranged on one side of the shell and communicated with the reaction bin; the water outlet is arranged on one side of the shell, which is far away from the water inlet, and is communicated with the reaction bin; the foam discharging port is arranged on the top side of the shell and communicated with the reaction bin. The utility model provides a high-efficient electrocatalytic oxidation reactor of modularization has the advantage that electrolytic reaction is abundant, long service life, security performance are high.
Description
Technical Field
The utility model relates to a sewage treatment device technical field especially relates to a high-efficient electrocatalytic oxidation reactor of modularization.
Background
With the continuous development of industry and science and technology, the electrolytic oxidation method or electrochemistry is used more and more widely in the treatment process of domestic sewage, industrial water and factory wastewater, and the method can not solve the problems of degradation of waste acid with high difficulty, conventional biochemical treatment, physicochemical treatment and the like. The advanced oxidation is also called as an electrocatalytic oxidation method, and has extremely high cost performance, wherein an electrode in the electrocatalytic oxidation method not only plays a role in transmitting current, but also plays a catalytic role in the oxidative degradation of organic matters, and the process is called as green water treatment because no pollution is caused. The method mainly removes COD in the wastewater by means of oxidation reaction on the surface of the anode, directly oxidizes and degrades organic matters on the surface of the anode, and directly or indirectly converts the organic matters in the wastewater into CO2 and water through electrochemical conversion. In the oxidation process, the anode potential must be higher than the decomposition potential of organic matters, so that two competing reactions of organic matter oxidation and oxygen evolution are carried out on the anode. The existing electrocatalytic oxidation equipment has low efficiency and large energy consumption in the electrolytic process and has a plurality of adverse factors. Such as: the existing electrocatalytic oxidation equipment adopts electric flocculation, an anode plate adopts an iron plate, a large amount of iron ions are generated in the electrolytic process, and a large amount of hazardous waste is generated in the subsequent treatment; at present, a titanium substrate is also adopted as an anode plate, the surface of the anode plate is coated with some active coatings, but in the electrolytic process, because acidic electrolyte permeates to a matrix, and part of oxygen generated in the electrolytic process is adsorbed on the surface of an electrode and continuously diffuses or migrates to the titanium matrix, permeates cracks of the active coatings, is adsorbed on the surface of the titanium substrate, and reacts with the titanium matrix to generate non-conductive TiO2, the conductivity of the electrode is deteriorated, the anode coating is passivated, and the service life of the anode plate is shortened; most of the existing electrocatalytic oxidation reactors adopt a single tank body, and waste liquid flows through an anode plate from top to bottom or from bottom to top to carry out oxidation reaction, so that the waste liquid cannot be completely oxidized at one time, and the treatment is poor; the upper openings of the existing tank bodies are open, a large amount of waste gas is generated in the electrolysis process, the working environment is poor, and the open type has electric shock danger in the operation process; the existing electrocatalytic oxidation equipment adopts a copper conducting system, and acid mist generated in the electrolytic process seriously corrodes the conducting system. The active radicals generated at the anode and the gas having oxidizing ability are less efficiently utilized in the electrolytic process, etc., and for the above reasons, there is a need for improvement.
Therefore, there is a need to provide a new modular high-efficiency electrocatalytic oxidation reactor to solve the above technical problems.
SUMMERY OF THE UTILITY MODEL
The utility model provides a technical problem provide a high-efficient electrocatalytic oxidation reactor of modularization.
In order to solve the technical problem, the utility model provides a high-efficient electrocatalytic oxidation reactor of modularization includes: a housing; a base disposed at a bottom side of the housing; the reaction bin is arranged in the shell; the water inlet is arranged on one side of the shell and communicated with the reaction bin; the water outlet is arranged on one side of the shell, which is far away from the water inlet, and is communicated with the reaction bin; a foam discharge port disposed at a top side of the housing, the foam discharge port being in communication with the reaction bin; the air outlet is arranged on the top side of the shell and positioned on one side of the foam discharging port, and the air outlet is communicated with the reaction bin; at least two modular titanium anode stacks, said modular titanium anode stacks being removably mounted within a housing; the liquid level observation transparent pipe is arranged on one side, close to the water inlet, of the shell, and the top end and the bottom end of the liquid level observation transparent pipe are communicated with the reaction bin.
Preferably, the water inlet is higher than the water outlet.
Preferably, the shell is close to one side of delivery port installs circulation inlet tube and circulation outlet pipe, the circulation inlet tube with the circulation outlet pipe is close to the one end in reaction storehouse all runs through the shell extends to in the reaction storehouse, the circulation inlet tube is located the top of circulation outlet pipe, the circulation inlet tube with the circulation outlet pipe all is connected with same circulating water pump.
Preferably, the circulating water inlet pipe and the circulating water outlet pipe are both closed at one end in the reaction bin, and a plurality of through holes are formed in the circulating water inlet pipe and the circulating water outlet pipe.
Preferably, the exhaust port is provided with a pressure relief safety valve.
Preferably, the modularized titanium anode group comprises a plurality of titanium substrates, the surface of each titanium substrate is coated with a high-oxidation overvoltage ceramic anode composite intermediate layer, the titanium substrates are assembled together in parallel through a support, and two conducting rods are mounted on the top sides of the titanium substrates.
Preferably, one end of the conductive rod, which is far away from the titanium substrate, is provided with a thread, the conductive rod is fixedly sleeved with a limiting plate, the conductive rod is sleeved with a sealing gasket ring, the conductive rod is in threaded connection with a nut, and the sealing gasket ring is located between the limiting plate and the nut.
Preferably, one side of shell is equipped with the seal groove, the seal groove is close to one side inner wall of shell be the opening and with the reaction bin is linked together, install the closing plate in the seal groove, the one end of conducting rod runs through the closing plate and extends to outside the seal groove, the limiting plate is located the closing plate is close to one side of reaction bin and with the closing plate contacts, the sealing backing ring with closing plate sealing connection, the closing plate with seal groove bolted connection.
Preferably, the seal groove is close to the ring channel has been seted up to one side of closing plate, the closing plate is close to one side fixed mounting of seal groove has the sealing washer, the sealing washer with ring channel sealing connection, the cover is equipped with the sealed cowling on the seal groove, two bar holes have been seted up to the symmetry on the sealed cowling, the conducting rod runs through the bar hole, the sealed cowling is close to one side fixed mounting of seal groove has the sealing strip, the sealing strip with seal groove sealing connection, fixed cover has connect the connecting plate on the seal groove, connecting plate and seal cowling bolted connection.
Compared with the prior art, the utility model provides a high-efficient electrocatalytic oxidation reactor of modularization has following beneficial effect:
1. the reaction bin is modularized, the modularized titanium anode groups are fully distributed at the bottom of the reaction bin, the volume ratio of the electrolytic reaction area to the sewage is large, and the electrolytic reaction is full;
2. the modularized titanium anode group in the reaction bin is of a modularized integral structure, and the modularized titanium anode group is detachably connected in the reaction bin, so that modules can be increased or decreased according to the production amount, and the disassembly and the assembly are convenient and quick;
3. the modularized titanium anode group adopts a titanium substrate, the surface of the titanium substrate is coated with a high oxidation overvoltage ceramic anode composite interlayer, the high oxidation overvoltage ceramic anode composite interlayer is prepared by a thermal decomposition method and mainly comprises platinum, precious platinum-titanium metal and composite materials of pt-TaO-TiO and SnO-SbO-Co-MnO oxide components, the high oxidation overvoltage ceramic anode composite interlayer is compact and has good diffusivity, and is uniformly covered on the surface of a titanium substrate, so that electrolyte is difficult to permeate to the surface of the titanium substrate, active oxygen precipitated in the electrolysis process is blocked from diffusing to the titanium substrate, the corrosion resistance of the coating is improved, the formation of a TiO oxide film is prevented, the modularized titanium anode group has good electrocatalytic activity and higher oxygen evolution overpotential, the conductivity is good, and the service life of the anode is prolonged, the method has extremely high electrolysis efficiency on the sewage COD, does not generate secondary pollution in the electrolysis process, and saves electricity and labor in the normal operation process;
4. the conductive rod is made of a titanium-copper composite material, so that the conductive rod has the conductivity of copper and the corrosion resistance of titanium, and the service life is prolonged;
5. the designed water flow direction is opposite to the gas overflow direction, a troposphere is formed in the operation process, the sewage can fully utilize active free radicals generated by electrolysis to oxidize harmful substances in the water, and the electrolysis efficiency is increased rapidly;
6. through discharging the foam mouth and gas vent, can discharge the harmful substance that the electrolysis produced and can in time discharge hazardous gas again, eliminate the potential safety hazard.
Drawings
FIG. 1 is a schematic structural view of a preferred embodiment of a modular high-efficiency electrocatalytic oxidation reactor provided by the present invention;
FIG. 2 is a side view of the structure of FIG. 1;
FIG. 3 is a schematic top view of the structure of FIG. 1;
FIG. 4 is a schematic structural view of the modular titanium anode stack shown in FIG. 1;
FIG. 5 is a side view of the modular titanium anode stack of FIG. 4;
FIG. 6 is a schematic structural view of a second embodiment of the modular high-efficiency electrocatalytic oxidation reactor provided by the present invention;
reference numbers in the figures: 1. the shell, 2, the base, 3, the reaction chamber, 4, the water inlet, 5, the delivery port, 6, the row's of foam mouth, 7, the gas vent, 8, the pressure release relief valve, 9, modularization titanium anode group, 10, the transparent tube is observed to the liquid level, 11, the circulation inlet tube, 12, the circulation outlet pipe, 13, the seal groove, 14, the titanium base plate, 15, the conducting rod, 16, the closing plate, 17, the limiting plate, 18, the sealing backing ring, 19, the nut, 20, the ring channel, 21, the sealing washer, 22, the seal cover, 23, the bar hole, 24, the sealing strip, 25, the connecting plate.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and embodiments.
The first embodiment:
referring to fig. 1-5, in a first embodiment of the present invention, a modular high efficiency electrocatalytic oxidation reactor comprises: a housing 1;
a base 2, the base 2 being disposed at a bottom side of the housing 1;
the reaction bin 3 is arranged in the shell 1;
the water inlet 4 is arranged on one side of the shell 1, and the water inlet 4 is communicated with the reaction bin 3;
the water outlet 5 is arranged on one side, away from the water inlet 4, of the shell 1, and the water outlet 5 is communicated with the reaction bin 3;
the foam discharging port 6 is arranged on the top side of the shell 1, the foam discharging port 6 is communicated with the reaction bin 3, and a large amount of organic foam overflows in the sewage electrolysis process;
the exhaust port 7 is arranged on the top side of the shell 1, the exhaust port 7 is positioned on one side of the foam discharging port 6, and the exhaust port 7 is communicated with the reaction bin 3, so that gas generated in the electrolysis process is discharged in time, and potential safety hazards caused by hydrogen enrichment are prevented;
at least two modular titanium anode groups 9, wherein the modular titanium anode groups 9 are detachably arranged in the shell 1;
the transparent pipe 10 is observed to the liquid level, the transparent pipe 10 is observed to the liquid level is installed the shell 1 is close to one side of water inlet 4, the top and the bottom of transparent pipe 10 are observed to the liquid level all with reaction bin 3 is linked together, is convenient for observe reaction bin 3 liquid level and the enrichment condition of producing the bubble in the electrolysis process.
The horizontal height of the water inlet 4 is higher than that of the water outlet 5, the design idea of conventional design that the water inlet is lower than the water outlet is broken, sewage enters the electrolysis system from top to bottom, but active gas generated in the electrolysis process overflows upwards, so that a troposphere is formed by the flow direction of water and the flow direction of gas, the reaction time of active substances and the sewage is fully prolonged, and the electrolysis efficiency is improved.
The circulating water inlet pipe 11 and the circulating water outlet pipe 12 are both closed at one end in the reaction bin 3, and a plurality of through holes are formed in the circulating water inlet pipe 11 and the circulating water outlet pipe 12.
And a pressure relief valve 8 is arranged on the exhaust port 7.
The modularized titanium anode group 9 comprises a plurality of titanium substrates 14, wherein the surface of the titanium substrate 14 is coated with a high-oxidation overvoltage ceramic anode composite intermediate layer, the high-oxidation overvoltage ceramic anode composite intermediate layer is compact, so that electrolyte is difficult to permeate the surface of a titanium substrate, the corrosion resistance of a coating against solution is improved, the modularized titanium anode group 9 has good electrocatalytic activity and high oxygen evolution overpotential, the modularized titanium anode group has extremely high electrolysis efficiency on sewage COD (chemical oxygen demand), the service life of an anode is prolonged, the titanium substrates 14 are assembled together in parallel through a support, and two conducting rods 15 are installed on the top side of the titanium substrates 14.
The high-oxidation overvoltage ceramic anode composite intermediate layer is a composite material which is prepared by a thermal decomposition method and contains pt-Ta2O5-TiO2 and SnO2-Sb2O5-Co-MnO oxide components, and the molar ratio of pt-Ta2O5-TiO2 is as follows: 1:5.5:10, wherein the molar ratio of SnO2-Sb2O5-Co-MnO is as follows: 11:1:6: 8.5; the surface hardness of the high oxidation overpotential ceramic anode composite intermediate layer is HRC (high hardness) 11, and the oxygen evolution overpotential is 1.93v (relative saturated calomel electrode); the thickness of the high-oxidation overvoltage ceramic anode composite intermediate layer is 6-8 microns.
The utility model discloses a titanium substrate 14, including conducting rod 15, fixed cover on conducting rod 15 has set up the screw thread, the conducting rod 15 is kept away from the one end of titanium substrate 14 is equipped with the limiting plate 17, the cover is equipped with sealing backing ring 18 on the conducting rod 15, threaded connection has nut 19 on the conducting rod 15, sealing backing ring 18 is located limiting plate 17 with between the nut 19.
One side of shell 1 is equipped with seal groove 13, seal groove 13 is close to one side inner wall of shell 1 be the opening and with reaction bin 3 is linked together, install closing plate 16 in the seal groove 13, the one end of conducting rod 15 runs through closing plate 16 and extend to outside the seal groove 13, limiting plate 17 is located closing plate 16 is close to one side of reaction bin 3 and with closing plate 16 contacts, sealing backing ring 18 with closing plate 16 sealing connection, closing plate 16 with seal groove 13 bolted connection.
The electrolysis power supply adopts a high-frequency pulse power supply, and peak current and peak voltage are formed in the electrolysis process, so that the electrolysis efficiency is improved, the energy consumption is reduced, and the wastewater treatment cost is reduced. The electrode has high electrocatalytic activity when electrolyzed in water solution, and adopts a high-frequency pulse power supply 'power supply-power failure-power supply' circulation operation device, continuously traps external electric field from O2 provided by the outside to provide electrons, forms oxygen radical ions O2-, finally generates H2O2 through a series of reactions, then decomposes the oxygen radical ions into extremely strong oxidant hydroxyl radical ions OH, destroys organic matters (COD) to generate charged organic 'fragments' and is degraded and removed. The main chemical reaction formula is as follows:
R+·OH→R·+H2O；
R·+M3+→M2++R+；
R++O2→ROO－→…→CO2+H2O。
wherein R represents an organic matter (COD), and M represents a catalyst metal element.
The main reason that the electrocatalytic oxidation method can efficiently remove pollutants in the wastewater is that the change of the electrocatalytic oxidation performance is not caused by external conditions such as voltage, current and the like, but is influenced by the electrode material. For the electrochemical treatment of the pollutants difficult to degrade, the most important is the design and preparation of electrode materials, and different electrode materials correspond to different conversion results and conversion mechanisms.
Compared with the prior art, the utility model provides a high-efficient electrocatalytic oxidation reactor of modularization has following beneficial effect:
1. the reaction bin 3 is modularized, the modularized titanium anode group 9 is fully distributed at the bottom of the reaction bin 3, the volume ratio of the electrolytic reaction area to the sewage is large, and the electrolytic reaction is full;
2. the modularized titanium anode group 9 in the reaction bin 3 is of a modularized integral structure, the modularized titanium anode group 9 is detachably connected in the reaction bin 3, modules can be increased or decreased according to the production amount, and the disassembly and the assembly are convenient and quick;
3. the modularized titanium anode group 9 adopts a titanium substrate 14, the surface of the titanium substrate 14 is coated with a high oxidation overvoltage ceramic anode composite intermediate layer, the high oxidation overvoltage ceramic anode composite intermediate layer is a composite material which is prepared by a thermal decomposition method and mainly comprises platinum, platinum-titanium noble metal, pt-Ta2O5-TiO2 and SnO2-Sb2O5-Co-MnO oxide components, the high oxidation overvoltage ceramic anode composite intermediate layer is compact and has good diffusivity, and is uniformly covered on the surface of the titanium substrate, so that the electrolyte is difficult to permeate to the surface of the titanium substrate, active oxygen separated out in the electrolytic process is blocked from diffusing to the titanium substrate, the corrosion resistance of the coating against solution is improved, the formation of a TiO2 oxide film is prevented, the modularized titanium anode group 9 has good electrocatalytic activity and higher oxygen evolution overpotential, the conductivity is good, and the service life of the anode is prolonged, the method has extremely high electrolysis efficiency on the sewage COD, does not generate secondary pollution in the electrolysis process, and saves electricity and labor in the normal operation process;
4. the conductive rod 15 is made of a titanium-copper composite material, so that the conductive rod has the conductivity of copper and the corrosion resistance of titanium, and the service life is prolonged;
5. the designed water flow direction is opposite to the gas overflow direction, a troposphere is formed in the operation process, the sewage can fully utilize active free radicals generated by electrolysis to oxidize harmful substances in the water, and the electrolysis efficiency is increased rapidly;
6. through the foam discharging port 6 and the exhaust port 7, harmful substances generated by electrolysis can be discharged, and dangerous gas can be discharged in time, so that potential safety hazards are eliminated.
Second embodiment:
based on the modular high-efficiency electrocatalytic oxidation reactor provided by the first embodiment of the application, the second embodiment of the application provides another modular high-efficiency electrocatalytic oxidation reactor. The second embodiment is merely a preferred way of the first embodiment, and the implementation of the second embodiment does not affect the implementation of the first embodiment alone.
The second embodiment of the present invention will be further explained with reference to the drawings and the embodiments.
Referring to fig. 6, the embodiment is different from the first embodiment in that an annular groove 20 is formed in one side of the sealing groove 13 close to the sealing plate 16, a sealing ring 21 is fixedly installed on one side of the sealing plate 16 close to the sealing groove 13, the sealing ring 21 is in sealing connection with the annular groove 20, a sealing cover 22 is sleeved on the sealing groove 13, two strip holes 23 are symmetrically formed in the sealing cover 22, the conductive rod 15 penetrates through the strip holes 23, a sealing strip 24 is fixedly installed on one side of the sealing cover 22 close to the sealing groove 13, the sealing strip 24 is in sealing connection with the sealing groove 13, a connecting plate 25 is fixedly sleeved on the sealing groove 13, and the connecting plate 25 is in bolted connection with the sealing cover 22.
Through the cooperation of sealing washer 21, sealing strip and sealed cover 22, increased the leakproofness of whole device, compare and seal through sealing gasket ring 18 alone, sealed effect is better.
The above only is the embodiment of the present invention, not limiting the scope of the present invention, all the equivalent structures or equivalent processes of the present invention are used in the specification and the attached drawings, or directly or indirectly applied to other related technical fields, and the same principle is included in the protection scope of the present invention.
Claims (9)
1. High-efficient electrocatalytic oxidation reactor of modularization, its characterized in that includes:
a housing;
a base disposed at a bottom side of the housing;
the reaction bin is arranged in the shell;
the water inlet is arranged on one side of the shell and communicated with the reaction bin;
the water outlet is arranged on one side of the shell, which is far away from the water inlet, and is communicated with the reaction bin;
a foam discharge port disposed at a top side of the housing, the foam discharge port being in communication with the reaction bin;
the air outlet is arranged on the top side of the shell and positioned on one side of the foam discharging port, and the air outlet is communicated with the reaction bin;
at least two modular titanium anode stacks, said modular titanium anode stacks being removably mounted within a housing;
the liquid level observation transparent pipe is arranged on one side, close to the water inlet, of the shell, and the top end and the bottom end of the liquid level observation transparent pipe are communicated with the reaction bin.
2. The modular high efficiency electrocatalytic oxidation reactor as set forth in claim 1, wherein said water inlet is at a higher level than said water outlet.
3. The modular efficient electrocatalytic oxidation reactor as set forth in claim 1, wherein a circulation water inlet pipe and a circulation water outlet pipe are installed on one side of said housing near said water outlet, one ends of said circulation water inlet pipe and said circulation water outlet pipe near said reaction chamber both penetrate said housing and extend into said reaction chamber, said circulation water inlet pipe is located above said circulation water outlet pipe, and said circulation water inlet pipe and said circulation water outlet pipe are both connected with the same circulation water pump.
4. The modular efficient electrocatalytic oxidation reactor as set forth in claim 3, wherein the ends of said circulating water inlet pipe and said circulating water outlet pipe located in said reaction chamber are both closed, and a plurality of through holes are opened on both said circulating water inlet pipe and said circulating water outlet pipe.
5. The modular high efficiency electrocatalytic oxidation reactor as set forth in claim 1, wherein said vent is fitted with a pressure relief safety valve.
6. The modular high efficiency electrocatalytic oxidation reactor as set forth in claim 1, wherein said modular titanium anode set comprises a plurality of titanium substrates coated with a high oxidation overvoltage ceramic anode composite intermediate layer on the surface thereof, said plurality of titanium substrates being assembled together in parallel by means of a bracket, and two current conducting rods being mounted on the top side of said plurality of titanium substrates.
7. The modular high-efficiency electrocatalytic oxidation reactor as set forth in claim 6, wherein one end of the conductive rod away from the titanium substrate is provided with a thread, the conductive rod is fixedly sleeved with a limiting plate, the conductive rod is sleeved with a sealing gasket ring, the conductive rod is in threaded connection with a nut, and the sealing gasket ring is located between the limiting plate and the nut.
8. The modularized high-efficiency electrocatalytic oxidation reactor as set forth in claim 7, wherein a sealing groove is formed on one side of the housing, an inner wall of the sealing groove on one side close to the housing is open and is communicated with the reaction chamber, a sealing plate is installed in the sealing groove, one end of the conductive rod penetrates through the sealing plate and extends out of the sealing groove, the limiting plate is located on one side of the sealing plate close to the reaction chamber and is in contact with the sealing plate, the sealing gasket ring is in sealing connection with the sealing plate, and the sealing plate is in bolted connection with the sealing groove.
9. The modularized high-efficiency electrocatalytic oxidation reactor as set forth in claim 8, wherein an annular groove is formed in one side of the sealing groove close to the sealing plate, a sealing ring is fixedly mounted on one side of the sealing plate close to the sealing groove, the sealing ring is in sealing connection with the annular groove, a sealing cover is sleeved on the sealing groove, two strip-shaped holes are symmetrically formed in the sealing cover, the conductive rod penetrates through the strip-shaped holes, a sealing strip is fixedly mounted on one side of the sealing cover close to the sealing groove, the sealing strip is in sealing connection with the sealing groove, a connecting plate is fixedly sleeved on the sealing groove, and the connecting plate is in bolted connection with the sealing cover.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202020756756.XU CN212246341U (en) | 2020-05-09 | 2020-05-09 | Modularized high-efficiency electrocatalytic oxidation reactor |
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| CN202020756756.XU CN212246341U (en) | 2020-05-09 | 2020-05-09 | Modularized high-efficiency electrocatalytic oxidation reactor |
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| CN212246341U true CN212246341U (en) | 2020-12-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210219 Address after: Block h, phase I, Baoji high end equipment Industrial Park, No. 95, Shuxiang Road South, Baoji hi tech Development Zone, Shaanxi Province, 721000 Patentee after: Baoji Titanium Prius Titanium Anode Technology Co.,Ltd. Address before: 721000 south section of Gaoxin 18th Road, high tech Development Zone, Baoji City, Shaanxi Province Patentee before: BAOJI CHANGLI SPECIAL METAL Co.,Ltd. |
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| TR01 | Transfer of patent right | ||
| CB03 | Change of inventor or designer information |
Inventor after: Li Qiao Inventor after: Qiao Zhihua Inventor before: Qiao Zhihua Inventor before: Li Qiao |
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| CB03 | Change of inventor or designer information |