CN1803580A - Technique for highly selective oxidation of carbon monoxide in hydrogen-enriched gas by light heat synergetic action - Google Patents
Technique for highly selective oxidation of carbon monoxide in hydrogen-enriched gas by light heat synergetic action Download PDFInfo
- Publication number
- CN1803580A CN1803580A CN 200610018323 CN200610018323A CN1803580A CN 1803580 A CN1803580 A CN 1803580A CN 200610018323 CN200610018323 CN 200610018323 CN 200610018323 A CN200610018323 A CN 200610018323A CN 1803580 A CN1803580 A CN 1803580A
- Authority
- CN
- China
- Prior art keywords
- carbon monoxide
- rich gas
- hydrogen
- light
- reactor
- 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
Abstract
The high-selective oxidating carbon monoxide in hydrogen-rich gas technique with light-thermal synergistic reaction comprises: with a light-catalyzed reaction installation, forcing the light source on loading noble metal nano catalyst surface with TiO2 or mixed oxide contained TiO2 as carrier, removing the carbon monoxide with synergistic reaction of light catalysis of TiO2 carrier and thermanl catalysis of noble metal. Wherein, the said light catalysis can restrain the thermal oxidation of noble metal to hydrogen. This invention also prolongs service lifetime of catalysts, needs not common heating device, and can be used in portable hydrogen fuel cell.
Description
Technical field
The present invention relates to the removal technology of CO (carbon monoxide converter) gas in the hydrogen-rich gas, a kind of specifically technology of utilizing the light heat synergetic action high-selectivity oxidation to remove carbon monoxide in the hydrogen-rich gas.
Background technology
Along with the continuous development of clean energy technology, be that the fuel cell technology of fuel is not developed rapidly because of not producing in its power generation process to pollute with hydrogen etc., in recent years in many aspects particularly electric automobiles be applied.The principle of work of hydrogen fuel cell is to be oxidized to water and chemical energy is changed into electric energy on platinum electrode by hydrogen.Wherein, hydrogen mainly is to be made through reactions such as direct part oxidation, steam reforming or steam conversion by methyl alcohol or other fuel, except that hydrogen, carbonic acid gas and water, also has a spot of CO in these rich hydrogen products.Because the hydrogen fuel cell electrode materials is generally platinum, the CO of trace just can make it poison, so the content of CO must be controlled at 100 * 10 in the hydrogen rich gas
-6Below the ppm.For this reason, hydrogen rich gas enters and carries out in the fuel cell before the oxidation, at first must remove CO wherein.
Fuel cell has that volume is little, in light weight, working temperature is low and characteristics such as stream time is long, the conventional method of removing CO all can't satisfy the requirement of fuel cell as physico-chemical processeses such as transformation absorption, low-temperature polymer membrane sepn, solvent absorbing, low temperature shift reaction and methanation reactions.And the selective oxidation reaction method is to add a spot of oxygen or air in hydrogen rich gas, selective catalytic oxidation CO under the specific catalyst effect, promptly when improving oxidation CO ability, reduce as far as possible or avoid hydrogen oxidized---promptly improve the selectivity of CO oxidation.At present, the catalyzer with selective oxidation CO is in the precious metals such as Pt, Pd, Rh, Ru, Au, Ag and Cu one or more to be loaded on the oxide carriers such as aluminum oxide, zeolite, ferric oxide, manganese oxide, zinc oxide make.As Pt/ γ-Al
2O
3Catalyst system, Pt/ zeolite catalysis system, Cu/Al
2O
3-MOx catalyst system and Au/MnOx catalyst system etc.These catalyzer under given conditions even can remove CO in the hydrogen at normal temperatures, but its selectivity is still not enough, the working conditions harshness, catalyzer also falls short of work-ing life, its range of application still is restricted.
Summary of the invention
The present invention has overcome the deficiency that simple thermocatalysis selective oxidation removal CO technology exists in the above-mentioned hydrogen rich gas, providing a kind of when improving oxidation CO ability, can reduce or avoid hydrogen oxidized---i.e. utilization can improve the optionally technology of carbon monoxide in the high selective oxidation hydrogen-rich gas of light heat synergetic action of CO oxidation.
Technical scheme of the present invention is as follows:
(1) photocatalysis is applied to the removal of CO (carbon monoxide converter) gas in the hydrogen rich gas.
(2) described photocatalytic reaction device is made up of reactor, photocatalyst and the light source of hollow, photocatalyst places in the cavity of reactor of described hollow, light source places around the described reactor, perhaps place inside reactor to directly act on catalyst surface, described photocatalyst is to be carrier and carried noble metal nanocatalyst that have normal temperature heat catalytic oxidation carbon monoxide with titanium dioxide or the mixed oxide that contains titanium dioxide; The concrete method of the carbon monoxide in the high selective oxidation hydrogen-rich gas flows through the cavity of the reactor of described photocatalytic reaction device for the hydrogen-rich gas that will contain carbon monoxide.
The present invention combines photocatalysis and thermocatalytic effect exactly, utilizes photocatalytic reaction device, by having the catalyzer of photocatalysis and thermocatalysis simultaneously, to improve the high selective oxidation of carbon monoxide in the catalyst treatment hydrogen rich gas.
Effect of the present invention and superiority are: (1) photochemical catalysis and thermocatalytic acting in conjunction help the oxidation of CO.Owing to applied light source at catalyst surface, light source can be by the photocatalysis oxidation CO of titania support in the catalyzer, can utilize simultaneously the heat heatable catalyst of light source self again, make that the heat catalytic oxidation CO effect of precious metal is given full play in the catalyzer.(2) photocatalysis of titanium dioxide can be restrained precious metal to H
2Thermal oxidation.CO is different with photochemical catalytic oxidation, and simple optically catalytic TiO 2 effect can not be with H
2Oxidation, and precious metal is to H
2The heat catalytic oxidation effect also can be restrained because of photocatalysis, thereby under photochemical catalysis and thermocatalytic acting in conjunction, improved the ability of oxidation CO, but reduce even avoided H
2Oxidation, thereby improved the transformation efficiency and the selectivity of CO oxidation.(3) compare with conventional thermocatalysis selective oxidation CO catalyzer, the photochemical catalytic oxidation CO effect of titania support self, also can improve the activity stability of loaded noble metal catalyst greatly, thereby prolong its work-ing life, this point is particularly important for the practical application of hydrogen fuel cell.Required heating unit when (4) device that adds fluorescent tube can be removed simple noble metal catalyst from and uses can satisfy characteristics such as hydrogen energy source battery volume is little, easy to carry, is particularly suitable for the hydrogen fuel cell in the power truck.
Embodiment:
Photocatalysis is applied to the removal of CO (carbon monoxide converter) gas in the hydrogen rich gas by photocatalytic reaction device.Described hydrogen rich gas is the hydrogen-rich gas in the hydrogen energy source battery.
Loading catalyst in a tubular reactor, reactor is by forming by uv-transmitting material, and as silica glass etc., the reactor periphery is provided with source of artificial light, or is directly exposed under the sunlight, constitutes a photo catalysis reactor.Source of artificial light also can place inside reactor, directly acts on catalyst surface, and this moment, reactor need not with seeing through ultraviolet material preparation.The wavelength of above-mentioned source of artificial light is 170～800nm, described photocatalyst is to be the carried noble metal nanocatalyst of carrier with titanium dioxide or the mixed oxide that contains titanium dioxide, precious metal composition wherein can be Pt, Pd, Rh, Ru, Au, in the precious metal such as Ag and Cu one or more, also can add other metals or rare earth element in the precious metal composition, the part by weight of other metals or rare earth element and precious metal is 1: 100～20: 100, and carrier is pure titinium dioxide or titanium dioxide and aluminum oxide, zeolite, ferric oxide, manganese oxide, one or more of oxide compounds such as zinc oxide mix.In other words, noble metal nano catalyzer that can low-temperature oxidation CO loads on it on carrier that contains titanium dioxide with photocatalysis and gets final product.Wherein, as long as content of titanium dioxide accounts for more than the 20wt%, the content of precious metal in photocatalyst is 0.1～15.0wt%, and catalyzer can be a solid granular, can be to load on another carrier with film or powder type.During concrete the use, the hydrogen-rich gas that contains CO is by the catalyzer in the reactor, and the CO in the hydrogen-rich gas fully is oxidized to CO under the acting in conjunction of precious metal heat catalytic oxidation and optically catalytic TiO 2 oxidation
2, and H
2Oxygenizement obtain very big supression because of the photocatalysis of titanium dioxide, thereby realize the high-selectivity oxidation of CO in the hydrogen rich gas.
One. contain oxide compound such as titanium dioxide and be carrier the carried noble metal nanocatalyst can be routinely the preparation method preparation of loaded catalyst, its purpose is exactly that noble metal nano particles with certain content loads on the pure titinium dioxide carrier or contains on the mixed oxide carrier of titanium dioxide.Method for preparing catalyst commonly used has sol-gel method, coprecipitation method, pickling process etc., also the TiO 2 sol type catalyzer that contains the precious metal composition can be loaded on by modes such as spraying, flood or lift and make the nanometer film catalyst on the particulate vectors such as glass, aluminum oxide, silicon oxide or activated carbon, also TiO 2 sol type catalyst cupport can made on the activated carbon felt-cloth.
Two. catalyzer is in the use of photo catalysis reactor
In the heat catalysis device of routine, remove heating unit, can uv-transmitting material and reactor is changed into, as silica glass etc., the reactor periphery is provided with the source of artificial light that wavelength is 170～800nm, or is directly exposed under the sunlight, constitutes a photo catalysis reactor.Source of artificial light also can place inside reactor, directly acts on catalyst surface, and this moment, reactor need not with seeing through ultraviolet material preparation.Then with the above-mentioned catalyst loading that makes in reactor, the form of catalyzer can be a particulate state, membranaceous, its objective is to allow catalyzer fully contact with reaction gas, simultaneously catalyzer can fully be exposed under the light source.When the hydrogen-rich gas that contains CO passed through reactor, the CO in the hydrogen-rich gas was oxidized to CO under the acting in conjunction of noble metal nano particles heat catalytic oxidation and optically catalytic TiO 2 oxidation
2, and H
2Oxygenizement obtain restraining because of the photocatalysis of titanium dioxide, thereby realize the high-selectivity oxidation of CO in the hydrogen rich gas.
The invention will be further described below in conjunction with embodiment.
Embodiment 1: the preparation of pure titinium dioxide colloidal sol
Be made into homogeneous solution in the deionized water with 150 milliliters of 1.1 milliliters of concentrated nitric acids (68%) addings, under violent stirring 17.0 milliliters titanium isopropylate is slowly splashed in the acidic aqueous solution, the suspension that contains white precipitate that hydrolysis obtains continues to stir the colloidal sols that form homogeneous transparent until the white precipitate dissolving down at 40 ℃.Colloidal sol packed into carry out dialysis with 2 liters of deionized waters in the dialyzer bag and handle, changing water to a dialysis water final pH value every 12 hours is 3.2.Colloidal sol is taken out from dialysis bag, make concentration and be about 3.5% TiO 2 sol.
Embodiment 2: the preparation of gold sol
Add the 200ml deionized water in the round-bottomed flask of 500ml, adding 0.5ml concentration is the HAuCl of 0.042g/ml
4.4H
2O solution is heated to boiling, and adding 4.0ml concentration is the sodium citrate solution of 0.011g/ml, heats 50min in the boiling water bath, moves in the reagent bottle after the cooling and preserves.Then this Au colloidal sol is passed through semi-permeable membranes dialysis twice, to remove unnecessary ion.Au content is about 0.01g/100ml in this colloidal sol, and the pH value is 5～6.
Embodiment 3:Au/TiO
2Preparation of catalysts
Get the TiO that Au colloidal sol 100ml that embodiment 2 makes and embodiment 1 make
2Colloidal sol 28.5ml mixes, and above-mentioned mixed sols 80 ℃ of oven dry, is risen to 400 ℃ by the speed of 4 ℃/min, and constant temperature 1h takes out after being cooled to room temperature.The content of Au is about 1.0wt% in this catalyzer, and high-resolution-ration transmission electric-lens (HRTEM) shows, TiO in this catalyzer
2Particle is about 10nm, and Au size of particles is about 20nm.
Embodiment 4:Au/TiO
2The performance evaluation of catalyzer
The Au/TiO that embodiment 3 is made
2Catalyzer grinds to form 30～50 orders, takes by weighing O.1 gram, be placed in the silica tube, and the ultraviolet lamp (254nm) of 3 4W of the peripheral 1 centimeters configuration of silica tube, it is 4.0% CO-He gas that 5ml content is successively injected in airtight back, the pure H of 5ml
2, CO concentration is 0.4% after the balance, H
2Concentration is about about 10%.Then, illumination was carried out 1 hour in the source of turning on the light, and sampling then is by separating after by TCD offline inspection CO and H through the TDX-01 packed column on the chromatographic instrument
2Concentration.In addition, carry out the reaction of another unglazed photograph, just, reactor is surrounded with aluminum slice, avoid light-illuminating turning on light simultaneously according to above-mentioned identical method.Above-mentioned both temperature when reacting all are controlled at about 50 ℃.Both are shown in Table 1 by reaction result.
Table 1 illumination and non-illumination are handled down and are contained H
2The result of-CO gas mixture
| Treatment condition | Result | |
| H 2Transformation efficiency, % | The transformation efficiency of CO, % | |
| Non-illumination/pure heat effect | 25.2 | 48.3 |
| Illumination/photo-thermal acting in conjunction | 0 | 100 |
The result shows in the table 1, compares according to effect with unglazed, and under the illumination effect, the transformation efficiency of CO brings up to 100% by 48.3%, and H
2Transformation efficiency drop to 0.0% by 25.2%.As seen, the illumination effect has improved the selectivity of the CO oxidation in the hydrogeneous atmosphere greatly.
Embodiment 5:Au/TiO
2The estimation of stability of catalyst activity
Press the method among the embodiment 4, react under illumination and non-illumination effect respectively, question response was tested the CO concentration in each autoreaction after 1 hour, obtained its transformation efficiency.Then replenish CO to initial concentration, reacted again 1 hour, survey CO concentration, obtain its transformation efficiency.Restock CO reacts.3 times so repeatedly, the relatively variation of the CO transformation efficiency under illumination and the non-illumination.Shown in its result's example table 2.
Table 2 illumination and non-illumination are handled down and are contained H
2The activity stability of-CO gas mixture relatively
| Treatment condition | The transformation efficiency of CO, % | ||
| The 1st time | The 2nd time | The 3rd time | |
| Non-illumination/pure heat effect | 48.3 | 39.0 | 31.3 |
| Illumination/photo-thermal acting in conjunction | 100 | 100 | 99.8 |
The result shows in the table 2, Au/TiO
2Catalyzer is under non-illumination effect, and the transformation efficiency of CO progressively descends, and its activity stability is relatively poor.And under the illumination effect, the transformation efficiency of CO does not almost descend, and shows good activity stability.
Claims (8)
1. the technology of carbon monoxide in the light heat synergetic action high-selectivity oxidation hydrogen rich gas is characterized in that: photocatalysis is applied to the removal of CO (carbon monoxide converter) gas in the hydrogen rich gas.
2. the technology of carbon monoxide in the light heat synergetic action high-selectivity oxidation hydrogen rich gas according to claim 1, it is characterized in that: described hydrogen rich gas is the hydrogen-rich gas that is applied in the hydrogen fuel cell.
3. the technology of carbon monoxide in the light heat synergetic action high-selectivity oxidation hydrogen rich gas according to claim 1 and 2, it is characterized in that: described photocatalysis is to realize by photocatalytic reaction device.
4. the technology of carbon monoxide in the light heat synergetic action high-selectivity oxidation hydrogen rich gas according to claim 3, it is characterized in that: described photocatalytic reaction device is by the reactor of hollow, photocatalyst and light source are formed, photocatalyst places in the cavity of reactor of described hollow, light source places around the described reactor, perhaps place inside reactor to directly act on catalyst surface, described photocatalyst is to be carrier and carried noble metal nanocatalyst that have normal temperature heat catalytic oxidation carbon monoxide with titanium dioxide or the mixed oxide that contains titanium dioxide; The concrete method of the carbon monoxide in the high selective oxidation hydrogen-rich gas flows through the cavity of the reactor of described photocatalytic reaction device for the hydrogen-rich gas that will contain carbon monoxide.
5. the technology of carbon monoxide in the light heat synergetic action high-selectivity oxidation hydrogen-rich gas according to claim 4, it is characterized in that: described light source is sunlight or source of artificial light, the illumination wavelength of described source of artificial light is that illumination wavelength is 170～800nm.
6. the technology of carbon monoxide in the light heat synergetic action high-selectivity oxidation hydrogen rich gas according to claim 4 is characterized in that: when described light source placed around the described reactor, described reactor adopts can uv-transmitting material to be made.
7. the technology of carbon monoxide in the light heat synergetic action high-selectivity oxidation hydrogen rich gas according to claim 6, it is characterized in that: described reactor adopting quartz glass is made.
8. the technology of carbon monoxide in the removal hydrogen rich gas according to claim 4, it is characterized in that: in the described carried noble metal nanocatalyst, precious metal is one or more among Pt, Pd, Rh, Ru, Au, Ag and the Cu, and described carrier is that in pure titinium dioxide or titanium dioxide and aluminum oxide or the oxide compounds such as zeolite or ferric oxide or manganese oxide or zinc oxide one or more mix.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610018323A CN100584744C (en) | 2006-01-23 | 2006-01-23 | Method for highly selective oxidation of carbon monoxide in hydrogen-enriched gas by light heat synergetic action |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610018323A CN100584744C (en) | 2006-01-23 | 2006-01-23 | Method for highly selective oxidation of carbon monoxide in hydrogen-enriched gas by light heat synergetic action |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1803580A true CN1803580A (en) | 2006-07-19 |
| CN100584744C CN100584744C (en) | 2010-01-27 |
Family
ID=36865763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200610018323A Active CN100584744C (en) | 2006-01-23 | 2006-01-23 | Method for highly selective oxidation of carbon monoxide in hydrogen-enriched gas by light heat synergetic action |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100584744C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102935364A (en) * | 2012-11-13 | 2013-02-20 | 福州大学 | Supported bimetallic catalyst for CO catalytic oxidation through visible light at room temperature |
| CN107020138A (en) * | 2017-05-09 | 2017-08-08 | 福州大学 | A kind of Supported Pd-Catalyst and its preparation method and application |
| CN112117020A (en) * | 2020-09-09 | 2020-12-22 | 中国工程物理研究院核物理与化学研究所 | Method for treating tritium water by photo-thermal concerted catalysis |
| CN112138537A (en) * | 2019-06-27 | 2020-12-29 | 奇鼎科技股份有限公司 | Preparation method of photocatalytic decomposition material and filter screen structure |
| CN113117675A (en) * | 2021-04-10 | 2021-07-16 | 福州大学 | Rhodium-erbium composite metal photo-thermal catalyst and preparation method and application thereof |
-
2006
- 2006-01-23 CN CN200610018323A patent/CN100584744C/en active Active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102935364A (en) * | 2012-11-13 | 2013-02-20 | 福州大学 | Supported bimetallic catalyst for CO catalytic oxidation through visible light at room temperature |
| CN102935364B (en) * | 2012-11-13 | 2014-04-30 | 福州大学 | Supported bimetallic catalyst for CO catalytic oxidation through visible light at room temperature |
| CN107020138A (en) * | 2017-05-09 | 2017-08-08 | 福州大学 | A kind of Supported Pd-Catalyst and its preparation method and application |
| CN107020138B (en) * | 2017-05-09 | 2019-06-07 | 福州大学 | A kind of Supported Pd-Catalyst and its preparation method and application |
| CN112138537A (en) * | 2019-06-27 | 2020-12-29 | 奇鼎科技股份有限公司 | Preparation method of photocatalytic decomposition material and filter screen structure |
| CN112138537B (en) * | 2019-06-27 | 2022-04-19 | 奇鼎科技股份有限公司 | Filter screen structure of photocatalytic decomposition material |
| CN112117020A (en) * | 2020-09-09 | 2020-12-22 | 中国工程物理研究院核物理与化学研究所 | Method for treating tritium water by photo-thermal concerted catalysis |
| CN112117020B (en) * | 2020-09-09 | 2022-11-22 | 中国工程物理研究院核物理与化学研究所 | Method for treating tritium water by photo-thermal concerted catalysis |
| CN113117675A (en) * | 2021-04-10 | 2021-07-16 | 福州大学 | Rhodium-erbium composite metal photo-thermal catalyst and preparation method and application thereof |
| CN113117675B (en) * | 2021-04-10 | 2022-04-08 | 福州大学 | Rhodium-erbium composite metal photo-thermal catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100584744C (en) | 2010-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Luengnaruemitchai et al. | Selective catalytic oxidation of CO in the presence of H2 over gold catalyst | |
| Tahir et al. | Dynamic photocatalytic reduction of CO2 to CO in a honeycomb monolith reactor loaded with Cu and N doped TiO2 nanocatalysts | |
| US8926937B2 (en) | Highly dispersed metal catalysts | |
| CN105457629A (en) | Load type nano precious metal catalyst and preparation method and application thereof | |
| Chen et al. | Selectively etching lanthanum to engineer surface cobalt-enriched LaCoO3 perovskite catalysts for toluene combustion | |
| US20050176580A1 (en) | Catalyst for partial oxidation of hydrocarbon, process for producing the same, process for producing hydrogen-containing gas with the use of the catalyst and method of using hydrogen-containing gas produced with the use of the catalyst | |
| Qi et al. | Platinum− copper bimetallic nanoparticles supported on TiO2 as catalysts for photo− thermal catalytic toluene combustion | |
| CN100584744C (en) | Method for highly selective oxidation of carbon monoxide in hydrogen-enriched gas by light heat synergetic action | |
| Chen et al. | Gas-phase total oxidation of nitric oxide using hydrogen peroxide vapor over Pt/TiO2 | |
| CN105597753B (en) | Three-dimensional ordered large-hole manganese acid lanthanum Supported Pt Nanoparticles tin nanocatalyst and its preparation method and application | |
| He et al. | Complete catalytic oxidation of o-xylene over CeO2 nanocubes | |
| CN107442117B (en) | A kind of exhaust gas catalytic conversion | |
| US20080241038A1 (en) | Preparation of manganese oxide-ferric oxide-supported nano-gold catalyst and using the same | |
| CN102658137B (en) | Cerium-zirconium-palladium nanopowder catalyst and preparation and application thereof | |
| US20150101923A1 (en) | Photocatalyst, method for preparation, photolysis system | |
| KR100614893B1 (en) | Method for preparing catalyst for carbon monoxide shift reaction | |
| US20080193354A1 (en) | Preparation of manganese oxide-cerium oxide-supported nano-gold catalyst and the application thereof | |
| Yin et al. | Promotion of Au (en) 2Cl3-derived Au/fumed SiO2 by treatment with KMnO4 | |
| CN110721685B (en) | Composite photocatalytic material and preparation method and application thereof | |
| CN102580725A (en) | Preparation method and application of nano monocrystal Pd core-shell catalyst | |
| CN101456584A (en) | Polyethyleneglycol-400 modified TiO2 powder and preparation method | |
| CN108714422B (en) | Mixed titanate nanoribbon supported metal palladium nanoparticle monolithic catalyst and preparation method and application thereof | |
| CN111111648A (en) | Preparation method of Pt nano particles | |
| CN115646499B (en) | Three-dimensional uniform porous copper-cerium catalyst for photo-thermal preferential oxidation of CO at room temperature | |
| Gunes et al. | Low temperature water-gas shift reaction on Au-CeO2/Al2O3 catalysts |
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 |