CN1328958A - Preparation of carbon nanometer pipe material and its equipment - Google Patents
Preparation of carbon nanometer pipe material and its equipment Download PDFInfo
- Publication number
- CN1328958A CN1328958A CN 01122772 CN01122772A CN1328958A CN 1328958 A CN1328958 A CN 1328958A CN 01122772 CN01122772 CN 01122772 CN 01122772 A CN01122772 A CN 01122772A CN 1328958 A CN1328958 A CN 1328958A
- Authority
- CN
- China
- Prior art keywords
- gas
- preparation
- plasma generator
- jet
- carbonaceous material
- 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
Landscapes
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a carbon nanometer pipe material and its equipment, and is characterized by that the said invention can adopt one-step method to implement the process of preparation of nanometer level catalyst granules, mixing catalyst and raw material and synthesizing carbon nanometer pipe material, i.e., utilizes the measures for directly injecting the carbon-contained material and catalyst granules into plasma jet to prepare carbon nanometer pipe material. The invented method features low raw material cost, simple and convenient operation, short technological process and stable working system, and possesses the extensive application field.
Description
One, technical field
The preparation of carbon nano-tube material and device belong to the crossing domain of coal science and applied science and Materials science, be specifically a kind of be a kind of method and apparatus that raw material using plasma jet means prepare carbon nano-tube material with the carbonaceous material.
Two, background technology
Carbon nanotube is a kind of type material of having found since 1991 (Ijima S., [Nature 354,56,1991]), is one of focus of paying close attention to of people to its preparation always.People such as Ebbesen (Ebbesen T. W., Ajayan P.M., [Nature, 356,1992]) adopt two graphite rods to be respectively anode and negative electrode, carry out direct-current discharge in 500 Torr atmosphere under 10～18V, 100A current condition.Anode constantly is consumed, and sediment pile is then constantly arranged on the negative electrode, and carbon nanotube is enclosed in formed settling inside.This method mainly is to rely on pyritous electric arc direct evaporation graphite rod, and the graphite raw material of use is also more expensive, and owing to there is the continuous consumption of electrode, so electric arc work is stable poor, the limitation of length of Graphite Electrodes this method move for a long time.Although Pang is (Pang L.S.K., Wilson M.A., [Energy﹠amp; Fuels, 7,436,1993]) also used coal to do raw material, but he still adopts coal-based rod as electrode, so its preparation method is similar with graphite/arc process.The method for preparing carbon nanotube in addition mainly also has catalystic pyrolysis (being called the CVD method again), is raw material but this method adopts acetylene, and is also relatively more expensive.
Three, summary of the invention
The purpose of carbon nano-tube material preparation of the present invention and device has been to overcome the shortcoming of raw material costliness in the above-mentioned prior art and has used raw material as the caused various defectives of electrode, thereby disclosing cheap coal, carbon materials, rubber powder and other carbonaceous material of a kind of direct employing is raw material, the technical scheme of synthesize nano carbon tube material and device under the situation that does not influence arc stability work.
The preparation method of a kind of carbon nano-tube material of the present invention, it is characterized in that it being a kind of with carbonaceous material and metal, metal oxide, nonmetal, nonmetal oxide catalyst mix, prepare the method for carbon nanotube by means among the plasma jet that carbonaceous material and granules of catalyst are directly sprayed into, just a synthetic step of the mixing of the preparation of nm-class catalyst particulate, catalyzer and raw material and carbon nanotube finishes.Its concrete steps and processing condition are:
Working gas hydrogen, argon gas, nitrogen and their mixed gas of I, feeding plasma generator are connected power supply and are also lighted plasma generator, and the electrode of plasma generator is a metallic substance,
II, feeding carrier gas argon gas, hydrogen, nitrogen, methane gas, oil liquefied gas; with being crushed to carbonaceous material below 200 orders and its weight percent is that 0～10% granules of catalyst mixes and injects directly in the arc plasma jet; under effect, promptly make carbon nano-tube material at jet
The processing condition that adopted in III, the preparation process: the producer operating power of DC arc plasma is 30～45kW; The plasma generator working gas is the mixed gas of hydrogen and argon gas, and their flow is respectively 4.2～6.2m
3/ h and 1.2～3.2m
3/ h; The employing argon gas is carrier gas, and flow is 0.7～2.7m
3/ h; For powder speed is 0.5～4.0g/s;
The carbonaceous material granularity is below 200 orders, and the working pressure of system is a normal pressure, the residence time 4～8ms.
The preparation of above-mentioned preparation carbon nano-tube material is characterized in that the carbonaceous material that uses is raw coal, carbon materials, rubber tyre and other carbonaceous material.
The preparation of above-mentioned preparation carbon nano-tube material is characterized in that described catalystic material comprises micron order and nano level Al, Ca, and Cu, Mn, Ni, Pt, Fe, Co, La, W, Au, metals such as Pd also comprise micron order and nanosize metal oxide LaO, Al
2O
3, Mo
2O
5, TiO
2, Fe
2O
3, CuO and non-metal particle Si, SiO
2
The preparation of above-mentioned preparation carbon nano-tube material is characterized in that the employed metal electrode material of plasma generator is Al, Ca, Cu, Mn, Ni, Pt, Fe, Co, La, W, Au, the Pd metallic substance, and with these materials preparation-obtained and alloy electrode.
The preparation of above-mentioned preparation carbon nano-tube material is characterized in that the hybrid mode of carbonaceous material and catalyzer is:
I. before spraying, carbonaceous material and micron order catalyzer are directly mixed, mixture directly sprays into as raw material among the plasma jet,
II. micron order catalyzer and carbonaceous material are by different position stream penetratings, and catalyzer sprays into the position and sprays into 20～50mm on the position at coal dust,
III. carbonaceous material is directly sprayed into, and the while is direct and electric arc splash-proofing sputtering metal electrode generation nm-class catalyst mixes in jet.
The device of realizing above-mentioned carbon nano-tube material preparation is characterized in that: primary device comprises plasma generator 1, feeder 2, reactor 3, collector more than 4 parts are formed, auxiliary unit has for powder part 8, the recirculated cooling water part, supplying unit 10 and air path part: hydrogen source gas 5, argon gas origin 6, for powder gas circuit 7 and balance gas circuit 9, from top to bottom, the order of connection of primary device is arc plasma generator 1 feeder 2 reactors 3 collectors 4, the exit diameter of arc plasma generator 1 is 10～20mm, feeder 2 tightly is positioned under the arc plasma generator 1, feeder 2 centre portionss are diameter plasma jet passages at 10～30mm, the jet that comes out from arc plasma generator 1 is from passing through here, it is the feed nozzle of 3～5mm that feeder 2 has two diameters, the vertical range of first nozzle distance arc plasma generator 1 jet exit is 15mm, the vertical range of first nozzle distance arc plasma generator 1 jet exit is 35～65mm, pass through nozzle, catalyzer and carbon compound can be directly by among the stream penetratings, and then under the feeder reactor 3, reactor 3 is a tubular structure, diameter is 10～30mm, and length is 300～350mm.
The advantage of the inventive method:
The electric arc jet that adopts among the present invention is produced by plasma generator, and it is a system that works alone, and the electrode of producer does not participate in the reaction that carbon nanotube generates; Raw material is admitted to jet area, rather than the work area of electric arc, so electric arc work is not subjected to it to disturb working stability.The electrode of producer is not consumed owing to synthesizing carbon nanotubes, so its cycle of operation is long, and raw material then can constantly infeed, so this method possesses the condition that serialization is produced.The raw material that adopts is a coal, and it is compared on cost with graphite and acetylene and takes advantage.
Four, description of drawings
Fig. 1 is a kind of device synoptic diagram for preparing the method for carbon nanotube of the present invention.
Number in the figure is: (1) dc arc plasma generator, and (2) feeder, (3) reactor, (4) collector, (5) hydrogen source gas, (6) argon gas source of the gas (7) is for powder gas circuit, (8) powder feeder, (9) balance gas circuit, (10) power supply.
Fig. 2 is the photo that utilizes institute of the present invention synthetic carbon nanotube that scanning electronic microscope is taken.
Fig. 3 is the high resolution photo that utilizes institute of the present invention synthetic carbon nanotube that transmission electron microscope is taken.
Five, the specific embodiment
Below in conjunction with figure and example the present invention will be described in detail:
Apparatus of the present invention mainly by arc plasma generator 1, feeder 2, reactor 3, Collector 4 and air feed part and power unit 10 form. Gas circuit comprise hydrogen source of the gas 5, Argon gas source of the gas 6, the signal that supplies powder gas circuit 7, powder feeder 8 and balance gas circuit 9. whole devices Figure is Fig. 1. reactor is tubular reactor, and reactor wall is graphite bushing, reactor Outer wall is the water-cooled chuck. After opening hydrogen source of the gas 5 and argon gas source of the gas 6 valves, plugged 10, light direct-current arc, the mist of hydrogen and argon gas forms later on plasma by electric arc Body jet, and open powder feeders 8 through feeder 2 and reactor 3. is for powder carrier gas 7 The raw material that drives lower powder feeder 8 outputs is injected in the plasma jet by feeder 2, and is flat The effect of weighing apparatus carrier gas 9 is the pressure between material bed within the balance powder feeder 8 up and down. Instead Should in reactor 3, carry out, in the graphite of a part of CNT in reactor 3 of generation Mix with coking material on the wall, in another part CNT of generation and the collector 4 Reaction residues mixes.
The employing shenfu coal is raw material, and coal powder size is about 200 orders after pulverizing. Adopt H2/ Ar arc plasma jet, the power of generator are 40kW; Hydrogen flowing quantity is 5.0m3/ h, argon flow amount are 1.8m3/ h, carrier gas flux are 1.2m3/ h; Supplying powder speed is 2.5g/s; Reaction After 5 minutes, big by observing in the deposit of ESEM on reactor graphite inwall Amount CNT (seeing Fig. 2).
Adopting the Baode coal is raw material, and coal powder size adds raw coal and weighs about 200 orders after pulverizing The iron powder of amount 5% is made catalyst. Adopt H2/ Ar arc plasma jet, the merit of generator Rate is 42kW; Hydrogen flowing quantity is 5.2m3/ h, argon flow amount are 2.2m3/ h, carrier gas is argon gas, flow is 1.7m3/ h; Supplying powder speed is 1.5g/s; React after 8 minutes, at reactor Can observe a large amount of CNTs by transmission electron microscope in the deposit on the graphite inwall. Carbon is received The external diameter of mitron is 100 nanometers, and internal diameter is 30 nanometers (seeing Fig. 3).
Adopting the Baode coal is raw material, and coal powder size adds raw coal and weighs about 200 orders after pulverizing The cobalt powder of amount 7% is made catalyst. Adopt H2/ Ar arc plasma jet, the merit of generator Rate is 40kW; Hydrogen flowing quantity is 5.2m3/ h, argon flow amount are 2.2m3/ h, carrier gas is argon gas, flow is 1.7m3/ h; Supplying powder speed is 3.0g/s; React after 10 minutes, by transmission Energy in the deposit of Electronic Speculum on reactor graphite inwall and in the pyrolysis residue in the collector Observe a kind of CNT material of special construction, the tube wall graphite synusia of this CNT it Between parallel to each other but with the axioversion of pipe, graphite synusia and axial angle are 25 °～30 °.
Embodiment 4
Adopting the Baode coal is raw material, and coal powder size adds the Al of raw coal weight 3% after pulverizing about 200 orders2O
3Powder is made catalyst. Adopt H2/ Ar arc plasma jet, generator Power be 45kW; Hydrogen flowing quantity is 5.2m3/ h, argon flow amount are 2.2m3/ h, carrier gas is argon gas, flow is 1.7m3/ h; Supplying powder speed is 1.6g/s; React after 6 minutes, by In the deposit of transmission electron microscope on reactor graphite inwall and the pyrolysis residue in the collector In can observe a large amount of CNTs.
Adopting the Baode coal is raw material, and coal powder size is about 200 orders, with raw coal and iron after pulverizing The powder catalyst sprays into plasma jet from different positions respectively, the position, position that catalyst sprays into In the lower 20mm place of arc plasma generator outlet, be positioned at coal dust and spray into 30mm on the place. Adopt H2/ Ar arc plasma jet, the power of generator are 42kW; Hydrogen flowing quantity is 5.2m3/ h, argon flow amount are 2.2m3/ h, the coal dust carrier gas is argon gas, flow is 1.7m3/ h; The catalyst carrier gas is argon gas, and flow is 2.1m3/ h; Supplying powder speed is 2.2g/s; Catalyst Feed rate is 0.18g/s; React after 5 minutes, by transmission electron microscope at reactor graphite inwall On deposit in and can observe a large amount of CNTs in the pyrolysis residue in the collector.
Adopting the Baode coal is raw material, after pulverizing coal powder size about 200 orders, with raw coal and CuO powder catalyst sprays into plasma jet from different positions respectively, the position that catalyst sprays into Setting in the lower 20mm place of arc plasma generator outlet, be positioned at coal dust and spray on the place 30mm. Adopt H2/ Ar arc plasma jet, the power of generator are 42kW; Hydrogen Flow is 5.2m3/ h, argon flow amount are 2.2m3/ h, the coal dust carrier gas is argon gas, flow is 1.7m3/ h; The catalyst carrier gas is argon gas, and flow is 2.1 m3/ h; Supplying coal dust speed is 3.6g/s; The feed rate of catalyst is 0.22g/s; React after 5 minutes, by transmission electron microscope at reactor Can observe a large amount of carbon in the deposit on the graphite inwall and in the pyrolysis residue in the collector Nanotube.
Claims (6)
1, a kind of preparation method of carbon nano-tube material, it is characterized in that it being a kind of with carbonaceous material and metal, metal oxide, nonmetal, nonmetal oxide catalyst mix, the method for preparing carbon nanotube by means among the plasma jet that carbonaceous material and granules of catalyst are directly sprayed into, just a synthetic step of the mixing of the preparation of nm-class catalyst particulate, catalyzer and raw material and carbon nanotube finishes, and its concrete steps and processing condition are:
Working gas hydrogen, argon gas, nitrogen and their mixed gas of I, feeding plasma generator are connected power supply and are also lighted plasma generator, and the electrode of plasma generator is a metallic substance,
II, feeding carrier gas argon gas, hydrogen, nitrogen, methane gas, oil liquefied gas; with being crushed to carbonaceous material below 200 orders and its weight percent is that 0～10% granules of catalyst mixes and injects directly in the arc plasma jet; under jet action, promptly make carbon nano-tube material
The processing condition that adopted in III, the preparation process: the producer operating power of DC arc plasma is 30～45kW; The plasma generator working gas is the mixed gas of hydrogen and argon gas, and their flow is respectively 4.2～6.2m
3/ h and 1.2～3.2m
3/ h; The employing argon gas is carrier gas, and flow is 0.7～2.7 m
3/ h; For powder speed is 0.5～4.0g/s; The carbonaceous material granularity is below 200 orders, and the residence time 4～8ms, the working pressure of system are normal pressure.
2, the device of realizing the described carbon nano-tube material preparation of claim 1 is characterized in that: primary device is by plasma generator (1), feeder (2), reactor (3), several parts of collector (4) are formed, auxiliary unit has for powder part (8), supplying unit (10) and air path part: hydrogen source gas (5), argon gas origin (6), for powder gas circuit (7) and balance gas circuit (9), from top to bottom, the order of connection of primary device is arc plasma generator (1) feeder (2) reactor (3) collector (4), the exit diameter of arc plasma generator (1) is 10～20mm, feeder (2) tightly is positioned under the arc plasma generator (1), feeder (2) centre portions is the plasma jet passage of diameter at 10～30mm, the jet that is come out by arc plasma generator (1) is from passing through here, it is the feed nozzle of 3～5mm that feeder (2) has two diameters, the vertical range of first nozzle distance arc plasma generator (1) jet exit is 15mm, the vertical range of second nozzle distance arc plasma generator (1) jet exit is 35～65mm, pass through nozzle, catalyzer and carbon compound can be directly by among the stream penetratings, and then under the feeder reactor (3), reactor (3) is a tubular structure, diameter is 10～30mm, and length is 300～350mm.
3. according to the preparation of the described carbon nano-tube material of claim 1, it is characterized in that the carbonaceous material that uses is raw coal, carbon materials, rubber tyre and other carbonaceous material.
4. according to the preparation of the described carbon nano-tube material of claim 1, it is characterized in that described catalystic material comprises micron order and nano level Al, Ca, Cu, Mn, Ni, Pt, Fe, Co, La, W, Au, metals such as Pd also comprise micron order and nanosize metal oxide LaO, Al
2O
3, Mo
2O
5, TiO
2, Fe
2O
3, CuO and non-metal particle Si, SiO
2
5. according to the preparation of the described carbon nano-tube material of claim 1, it is characterized in that the employed metal electrode material of plasma generator is Al, Ca, Cu, Mn, Ni, Pt, Fe, Co, La, W, Au, the Pd metallic substance, and with the preparation-obtained alloy electrode of these materials.
6. according to the preparation of the described carbon nano-tube material of claim 1, it is characterized in that the hybrid mode of carbonaceous material and catalyzer:
I, before spraying, carbonaceous material and micron order catalyzer are directly mixed, mixture directly sprays into as raw material among the plasma jet,
II, micron order catalyzer and carbonaceous material are by different position stream penetratings, and catalyzer sprays into the position and sprays into 20～50mm on the position at coal dust,
III, carbonaceous material is directly sprayed into, and simultaneously directly and electric arc splash-proofing sputtering metal electrode generation nm-class catalyst in jet, mix.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01122772A CN1093507C (en) | 2001-07-22 | 2001-07-22 | Preparation of carbon nanometer pipe material and its equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01122772A CN1093507C (en) | 2001-07-22 | 2001-07-22 | Preparation of carbon nanometer pipe material and its equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1328958A true CN1328958A (en) | 2002-01-02 |
| CN1093507C CN1093507C (en) | 2002-10-30 |
Family
ID=4664890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01122772A Expired - Fee Related CN1093507C (en) | 2001-07-22 | 2001-07-22 | Preparation of carbon nanometer pipe material and its equipment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1093507C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003095362A3 (en) * | 2002-05-09 | 2004-04-08 | Inst Nat Rech Scient | Method and apparatus for producing single-wall carbon nanotubes |
| WO2004046030A1 (en) * | 2002-11-15 | 2004-06-03 | Mgill University | Method for producing carbon nanotubes using a dc non-transferred thermal plasma torch |
| CN100484869C (en) * | 2006-08-11 | 2009-05-06 | 中国科学院等离子体物理研究所 | Method for preparing carbon nano tube using high power plasma generator |
| CN101531362B (en) * | 2009-04-17 | 2010-11-10 | 北京化工大学 | Method for one-step growth of carbon nanotube by taking carbon composite as catalyst |
| CN106276846A (en) * | 2016-07-15 | 2017-01-04 | 华北电力大学 | A kind of system and method preparing CNT |
| CN107275113A (en) * | 2017-06-08 | 2017-10-20 | 中国科学院电工研究所 | The method that double medium agent jet plasmas prepare flexible super capacitor combination electrode |
| CN108927143A (en) * | 2018-09-06 | 2018-12-04 | 王淑英 | A kind of preparation method for treating open-angle glaucoma pharmaceutical intermediate |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2546511B2 (en) * | 1993-08-26 | 1996-10-23 | 日本電気株式会社 | Method for synthesizing fullerene and carbon nanotube |
| JPH11116218A (en) * | 1997-10-17 | 1999-04-27 | Osaka Gas Co Ltd | Production of single layered nanotube |
| CN1093508C (en) * | 1999-06-16 | 2002-10-30 | 中国科学院金属研究所 | Method for preparing single wall nanometer carbon tube hydrogen storage material |
-
2001
- 2001-07-22 CN CN01122772A patent/CN1093507C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003095362A3 (en) * | 2002-05-09 | 2004-04-08 | Inst Nat Rech Scient | Method and apparatus for producing single-wall carbon nanotubes |
| WO2004046030A1 (en) * | 2002-11-15 | 2004-06-03 | Mgill University | Method for producing carbon nanotubes using a dc non-transferred thermal plasma torch |
| CN100484869C (en) * | 2006-08-11 | 2009-05-06 | 中国科学院等离子体物理研究所 | Method for preparing carbon nano tube using high power plasma generator |
| CN101531362B (en) * | 2009-04-17 | 2010-11-10 | 北京化工大学 | Method for one-step growth of carbon nanotube by taking carbon composite as catalyst |
| CN106276846A (en) * | 2016-07-15 | 2017-01-04 | 华北电力大学 | A kind of system and method preparing CNT |
| CN107275113A (en) * | 2017-06-08 | 2017-10-20 | 中国科学院电工研究所 | The method that double medium agent jet plasmas prepare flexible super capacitor combination electrode |
| CN108927143A (en) * | 2018-09-06 | 2018-12-04 | 王淑英 | A kind of preparation method for treating open-angle glaucoma pharmaceutical intermediate |
| CN108927143B (en) * | 2018-09-06 | 2020-01-03 | 北京宝诺康医药科技有限公司 | Preparation method of pharmaceutical intermediate for treating open-angle glaucoma |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1093507C (en) | 2002-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Awasthi et al. | Synthesis of carbon nanotubes | |
| Planeix et al. | Application of carbon nanotubes as supports in heterogeneous catalysis | |
| Moothi et al. | Coal as a carbon source for carbon nanotube synthesis | |
| US20100072430A1 (en) | Compositions of carbon nanosheets and process to make the same | |
| JP2526782B2 (en) | Carbon fiber and its manufacturing method | |
| US20100064973A1 (en) | Apparatus and method for making carbon nanotube array | |
| US7700048B2 (en) | Apparatus for making carbon nanotube array | |
| CN1751989A (en) | Method of preparing carbon nanocages | |
| CN1738767A (en) | Method for producing carbon nanotubes using a DC non-transferred thermal plasma torch | |
| US7052667B2 (en) | RF plasma method for production of single walled carbon nanotubes | |
| CN1093507C (en) | Preparation of carbon nanometer pipe material and its equipment | |
| Somanathan et al. | Helical multiwalled carbon nanotubes (h-MWCNTs) synthesized by catalytic chemical vapor deposition | |
| CN1886333A (en) | Method for the preparation of high purity carbon nanotubes using water | |
| Wang et al. | Formation of carbon nanotubes from polyvinyl alcohol using arc-discharge method | |
| CN1248248C (en) | Technology and equipment for preparing magnetic carbon nanometer tube by plasma | |
| Choi et al. | Continuous process of carbon nanotubes synthesis by decomposition of methane using an arc-jet plasma | |
| Tian et al. | Effect of catalysis on coal to nanotube in thermal plasma | |
| Tepale-Cortés et al. | Multi-walled carbon nanotubes synthesis by arc discharge method in a glass chamber | |
| CN100484869C (en) | Method for preparing carbon nano tube using high power plasma generator | |
| Khan et al. | Carbon nanotube and its possible applications | |
| Xinghui et al. | Large-area carbon nanotubes film synthesized for field emission display by special CVD equipment and the field emission properties | |
| CN1174917C (en) | Nanometer carbon pipe material and its preparation | |
| Chung | Effect of H~ 2 on Formation Behavior of Carbon Nanotubes | |
| CN111362253B (en) | Carbon nano tube prepared by catalytic cracking of hydrocarbon by gas-phase damping method, device and method | |
| CN1522956A (en) | Process for preparing nanometer carbon microballoon by arc discharging technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1037479 Country of ref document: HK |