CN1270081A - Efficient catalyst for synthesizing ammonia and its preparing process - Google Patents
Efficient catalyst for synthesizing ammonia and its preparing process Download PDFInfo
- Publication number
- CN1270081A CN1270081A CN99112843A CN99112843A CN1270081A CN 1270081 A CN1270081 A CN 1270081A CN 99112843 A CN99112843 A CN 99112843A CN 99112843 A CN99112843 A CN 99112843A CN 1270081 A CN1270081 A CN 1270081A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- ruthenium
- ammonia
- auxiliary agent
- synthesizing ammonia
- 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
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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
A catalyst for effectively synthesizing ammonia is composed of carrier (activated carbon) and active component which is composed of Ru (0.1-16 wt.%) and assistant (alkali-earth metal, rare-earth metal or alkali alloy) in mole ratio of 0.01-10. Said catalyst is prepared through immersing carrier in solution containing Ru compound, reducing at 200-500 deg.C for 30 min-5 hr under hydrogen atmosphere, and dipping solution of alkali-earth, rare-earth or alkali metal. It can be used to synthesize ammonia with nitrogen and hydrogen under lower temp and pressure.
Description
The present invention relates to a kind of is active component with the noble ruthenium, and alkaline earth/rare earth/alkali metal oxide is or/and hydroxide is auxiliary agent, and business-like absorbent charcoal material (AC) is high activity new ammonia synthesis catalyst of carrier and preparation method thereof.
Ammonia synthesis catalyst is a most important catalyst in the ammonia synthesizing industry.It directly affects the output and the economic benefit of synthetic ammonia, also affects the operating condition of production of synthetic ammonia simultaneously.Traditional ammonia synthesis catalyst is with aluminium oxide, and potassium oxide etc. are the fused iron catalyst of auxiliary agent, its operating pressure (10～30MPa) and operating temperature (450～550 ℃) all higher.In addition, though very ripe technically with fused iron catalyst synthetic ammonia under higher temperature and pressure, this process energy consumption height, harsh to the material requirement of equipment, operating flexibility is poor.Therefore it is very necessary reducing the ammonia synthesis temperature and pressure.It is precursor by ruthenium trichloride that U.S.Patent 4 600 571 has narrated a kind of, the ruthenium-based catalyst that the active graphite charcoal of high temperature specially treated is a carrier.Wherein active graphite charcoal is had the specially treated requirement, the ruthenium loading is greater than 6%.This catalyst can be used for ammonia synthesis reaction.U.S.Patent 4,142 993 has described a kind of ammonia synthesis ruthenium-based catalyst, and its preparation route is as follows: the charcoal carrier is the dipping auxiliary agent earlier, and vacuum baking floods ruthenium trichloride again, makes catalyst through vacuum baking etc. again.Its preparation technology is loaded down with trivial details, and preparation facilities is rare, more difficult industrialization.In the method for preparing catalyst of U.S.Patent 3 830 753 narrations, the auxiliary agent of ruthenium-based catalyst adopts the alkali metal vacuum evaporation deposition to catalyst.This method industrial be infeasible.
The object of the present invention is to provide a kind of new and effective ammonia synthesis catalyst and preparation method thereof, this catalyst has under lower temperature and pressure the ability that nitrogen and hydrogen is converted into ammonia.
The invention provides a kind of efficient catalyst for synthesizing ammonia, be made up of carrier and active ingredient, it is characterized in that: carrier is an absorbent charcoal material; With ruthenium is main active ingredient, and loading is 0.1～16%wt, is auxiliary agent with alkaline-earth metal, rare earth metal, alkali alloy, and ruthenium and auxiliary agent mol ratio are 0.01～10.Best ruthenium loading is 0.1～8%wt among the present invention.
Preparation of catalysts method of the present invention is earlier with containing the ruthenium compound solution impregnating carrier; Reduction is 30 minutes～5 hours under 200～500 ℃ of nitrogen atmosphere; Flood alkaline earth, rare earth or alkali metal soln again and make auxiliary agent.
The active component precursor is selected from ruthenium trichloride, ruthenium, ruthenate and organic ruthenium; Maceration extract is water or organic solution, and organic solvent is selected from methyl alcohol, ethanol, cyclohexane.
The auxiliary agent precursor is selected from alkaline earth, rare earth, alkali-metal nitrate, hydroxide, carbonate, halide.
Absorbent charcoal material is selected from charcoal fiber, carbon molecular sieve, how empty graphite carbon nanotube.
Catalyst of the present invention can be used for the ammonia synthesis in various ammonia synthesis factory, the especially chemical fertilizer industries or under the prerequisite that does not change existing ammonia synthesizer, the catalytic reactor of connecting also can improve the ammonia yield.
The Preparation of catalysts condition has remarkable influence to its ammonia synthesis activity.Among the present invention, the preparation condition (loading, amount of auxiliary and kind, prereduction temperature, carrier and preparation order) that is supported on the ruthenium-based catalyst on the business-like active carbon is investigated activity influence.
The ammonia synthesis reaction condition also has material impact to the yield of ammonia.Reaction temperature, the volume space velocity of reaction pressure and gas is investigated.
Below by embodiment in detail the present invention is described in detail.
Example 1
Ruthenium trichloride is mixed with maceration extract in the water-soluble or organic solvent (methyl alcohol, ethanol, cyclohexane etc.), adds the spin coating 4～5 hours on rotary evaporator of active carbon (AC) or charcoal fiber (CF) carrier.The specific surface of absorbent charcoal carrier is 1293m
2/ g, the specific surface of charcoal fiber carrier are 844m
2/ g.Then in 120 ℃ of oven dry 10 hours, 200～500 ℃ of prereduction 4～5 hours under nitrogen atmosphere.Flood auxiliary agent (B) KOH (or KNO again
3, Ba (NO
3)
2, Ce (NO
3)
36H
2O, La (NO
3)
36H
2O) the aqueous solution is then 120 ℃ of dryings 10 hours.Make Ru-B/AC and Ru-B/CF catalyst respectively.
Change the addition of ruthenium trichloride and auxiliary agent, can make serial ammonia synthesis catalyst with different Ru/B ratios.
Example 2
Ammonia synthesis performance evaluation is carried out in the stainless steel reaction pipe.Catalyst amount 0.5 gram, granularity 40～60 orders, reaction gas are nitrogen and hydrogen gaseous mixture, its nitrogen hydrogen ratio is 1: 3.Catalyst ammonia synthesis reaction performance to example 1 preparation is estimated, reaction pressure 3.0MPa, and reaction temperature is 400 ℃.Under the reaction condition identical with example 2 an industrial ammonia synthesis fused iron catalyst has been carried out the ammonia synthesis performance test, its comparative result is listed in table 1.
Table 1 reflects the concentration (V%) of ammonia in the implication
Gaseous mixture volume air speed (hr
-1) catalyst
2,000 3,000 6000 10000Ru (4wt%)-K/AC 3.76Ru (4wt%)-Ba/AC 6.56 5.74 4.75 4.35 fused iron catalysts 3.91 3.42 2.90 2.60
The result shows that the ammonia synthesis specific activity industry ammonia synthesis fused iron catalyst activity of Ru of the present invention (4wt%)-K/AC and Ru (4wt%)-Ba/AC catalyst is much higher.When reaching identical outlet ammonia concentration, the volume space velocity of catalyst of the present invention can improve more than 5 times, and the clean yield of corresponding ammonia can increase substantially.
Example 3
To the Ru-K/AC catalyst, at gaseous mixture volume air speed 3000hr
-1And under the reaction pressure 3.0MPa condition, having investigated of the influence of ruthenium loading to the ammonia synthesis activity, the result is as shown in table 2.
Table 2 is in the Ru-K/AC of different ruthenium loadings catalyst upper outlet ammonia concentration (V%)
Ruthenium loading (wt%) reaction temperature (℃)
2.0 4.0 6.0 8.0350 0.11 3.76 0.75 1.90375 0.26 2.16 3.15 3.75400 0.65 3.76 4.27 5.10425 1.51 5.29 5.48 5.68450 2.93 4.81 4.20 4.45
As can be seen from Table 2, under the used reaction condition of the present invention, along with the ammonia concentration of increasing export of ruthenium loading is increasing than under the low reaction temperatures.Along with the increase of reaction temperature, outlet ammonia concentration increases earlier, is issued to maximum to uniform temperature, reduces then.For the ruthenium loading is that 8% the highest ammonia exit concentration of catalyst can reach 5.68%.
Example 4
For Ru (4wt%)/AC catalyst, at gaseous mixture volume air speed 3000hr
-1, reaction pressure 3.0MPa and reaction temperature are under 400 ℃ of conditions, have investigated auxiliary agent type and KOH and Ba (NO
3)
2Amount to the influence of ammonia synthesis activity.It the results are shown in table 3.
Table 3 auxiliary agent is to the influence of ammonia exit concentration (V%)
The Ru/B mol ratio
The auxiliary agent precursor
0.16 0.50 1.0 2.0
KNO
3 1.82 - - -
KNO
3Preliminary treatment 3.05---
KOH 3.76 0.34 0.26 0.13
Ce(NO
3)
3 1.69 - - -
Ce (NO
3)
3Preliminary treatment 1.88---
La(NO
3)
3 1.78 - - -
La (NO
3)
3Preliminary treatment 1.96---
Ba(NO
3)
2 5.73 4.77 4.67 3.95
Ba (NO
3)
2Preliminary treatment 5.86---
As seen from table, along with the Ru/B mol ratio increases, the perhaps minimizing of amount of auxiliary, catalyst activity lowers.Amount of auxiliary is to the active important influence of ammonia synthesis.At the auxiliary agent K of research, Ce, La, among the Ba, active best with Ba.Catalyst can suitably improve activity with nitrogen preliminary treatment at a certain temperature before use.
Example 5
For the ruthenium loading is the 4wt% catalyst, has investigated the effect of different raw material of wood-charcoal material.The raw material of wood-charcoal material that adopts is a carbon molecular sieve, active carbon and carbon fiber etc.At gaseous mixture volume air speed 3000hr
-1, reaction pressure 3.0MPa and reaction temperature are under 400 ℃ of conditions, have investigated the influence of carrier raw material of wood-charcoal material to the ammonia synthesis activity.Its result is as shown in table 4.
The physical arrangement of table 4 raw material of wood-charcoal material and ammonia synthesis reaction active carrier raw material of wood-charcoal material specific surface average pore size pore volume auxiliary agent outlet ammonia
(m
2/ g) (A) (cm
3/ g) concentration V% active carbon 1293.1 14.9 0.65 KOH 3.76
KNO
3 1.82
Ba (NO
3)
25.73 carbon molecular sieve 14.3 15.2 0.007 KOH 0.06
KNO
3 0.06
Ba (NO
3)
20.09 carbon fiber 844.7 14.4 0.40 Ba (NO
3)
21.82
As seen from Table 4, the ammonia synthesis activity has shown bigger difference on different carriers.The ammonia synthesis activity is preferable on active carbon, and carbon fiber takes second place, and carbon molecular sieve is relatively poor.This may be because the specific surface of carbon molecular sieve is lower.
Example 6
For Ba (NO
3)
2With KOH be the ruthenium activated-carbon catalyst system of auxiliary agent, also investigated the influence of preparation procedure.Method 1 adopts dipping ruthenium trichloride earlier, floods auxiliary agent again; Method 2 adopts earlier floods active component behind the dipping auxiliary agent.At gaseous mixture volume air speed 3000hr
-1, reaction pressure 3.0MPa and reaction pressure are that its reaction result is as follows under 400 ℃ of conditions:
The ammonia synthesis activity of the catalyst of the different preparation method's gained of table 5
Outlet ammonia concentration V% auxiliary agent
Method 1 method 2 Ba (NO
3)
25.73 3.66
KOH 3.76 0.37
Example 7
It is necessary reducing with reducing agent behind the dipping ruthenium trichloride in method 1.Therefore, we have studied the influence of reduction temperature to catalyst ammonia synthesis activity.Reduction temperature is between room temperature and 500 ℃, and the catalyst ammonia synthesis activity of preparation is as shown in table 6.
Table 6 reduction temperature to catalyst ammonia synthesis activity influence reduction temperature (℃) 0 200 300 400 500 outlet ammonia concentration (V%) 3.61 4.60 4.76 5.73 4.95
Table 6 data are that Ru (4wt%)-Ba/AC catalyst under the different prereduction temperature is at volume space velocity 3000hr
-1, reaction pressure 3.0MPa and reaction temperature are 400 ℃ of reaction results under the condition.
Example 8
For Ru (the 4wt%)/AC catalyst of preparation, we have investigated the influence of reaction condition to its ammonia synthesis activity.Table 7 has provided the catalyst ammonia synthesis catalytic activity under the differential responses temperature.
Table 7 reaction temperature is to the ammonia synthesis activity of Ru (4wt%)/AC catalyst
(air speed 3000hr
-1, 3.0MPa)
Outlet ammonia concentration (V%) catalyst
350℃ 375℃ 400℃ 425℃ 450℃Ru(4wt％)-K/AC 0.62 2.16 3.76 5.19 4.88Ru(4wt％)-Ba/AC 1.79 2.78 5.74 4.88 4.27
On show to show and illustrated that different auxiliary agents have different optimum operating temperatures.The catalyst optimal reaction temperature of potassium promoter is at 425 ℃, and the catalyst optimum operating temperature of barium auxiliary agent is at 400 ℃.Obviously the ammonia synthesis catalyst of barium auxiliary agent has high activity at a lower temperature.
Example 9
It is the result of the influence of ammonia synthesis catalyst activity to ruthenium that table 8 has provided reaction pressure.Catalyst is to Ru (4wt%)-Ba/AC; Reaction temperature is 400 ℃, volume space velocity 3000hr
-1
Table 8 reaction pressure to ruthenium be the ammonia synthesis catalyst activity influence reaction pressure (MPa) 1.0 3.0 5.0 7.0 outlet ammonia concentration (V%) 2.48 5.75 7.05 8.30
As seen from the above table, with the rising of reaction pressure, outlet ammonia concentration is increase trend.But along with the increase of pressure, outlet ammonia concentration increasing degree diminishes.Can predict that too high pressure has increased energy consumption, preferable reaction pressure is below 10.0MPa.Therefore, this catalyst can be used for not changing under the prerequisite of existing ammonia synthesizer, and the catalytic reactor of connecting also can improve the ammonia yield.
Example 10
We have also investigated the effect of reaction volume air speed on Ru (4wt%)-Ba/AC catalyst, and other reaction conditions are: temperature 350 and 400 ℃, pressure 3.0MPa.Reaction result is as follows:
Table 9 volume space velocity is to influence (the outlet ammonia concentration V%) volume space velocity (hr of catalyst ammonia synthesis activity
-1) 2,000 3,000 6,000 10000
350℃ 2.21 1.79 1.56 1.25
400℃ 6.56 5.75 4.75 3.62
As seen from table, catalyst of the present invention has high activity in broad air speed scope.Therefore, this catalyst can be used for the air speed scope of broad.
Claims (6)
1. an efficient catalyst for synthesizing ammonia is made up of carrier and active ingredient, it is characterized in that: carrier is an absorbent charcoal material; With ruthenium is main active ingredient, and loading is 0.1～16%wt, is auxiliary agent with alkaline-earth metal, rare earth metal, alkali alloy, and ruthenium and auxiliary agent mol ratio are 0.01～10.
2. according to the described efficient catalyst for synthesizing ammonia of claim 1, it is characterized in that: the ruthenium loading is 0.1～8%wt.
3. the preparation method of the described efficient catalyst for synthesizing ammonia of claim 1 is characterized in that: earlier with containing the ruthenium compound solution impregnating carrier; Reduction is 30 minutes～5 hours under 200～500 ℃ of nitrogen atmosphere; Flood alkaline earth, rare earth or alkali metal soln again and make auxiliary agent.
4. according to the preparation method of the described efficient catalyst for synthesizing ammonia of claim 3, it is characterized in that: the active component precursor is selected from ruthenium trichloride, ruthenium, ruthenate and organic ruthenium, maceration extract is water or organic solution, and organic solvent is selected from methyl alcohol, ethanol, cyclohexane.
5. according to the preparation method of the described efficient catalyst for synthesizing ammonia of claim 3, it is characterized in that: the auxiliary agent precursor is alkaline earth, rare earth, alkali-metal nitrate, hydroxide, carbonate, halide.
6. according to the preparation method of the described efficient catalyst for synthesizing ammonia of claim 3, it is characterized in that: absorbent charcoal material is selected from charcoal fiber, carbon molecular sieve, how empty graphite carbon nanotube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991128435A CN1133493C (en) | 1999-04-14 | 1999-04-14 | Efficient catalyst for synthesizing ammonia and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991128435A CN1133493C (en) | 1999-04-14 | 1999-04-14 | Efficient catalyst for synthesizing ammonia and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1270081A true CN1270081A (en) | 2000-10-18 |
| CN1133493C CN1133493C (en) | 2004-01-07 |
Family
ID=5276096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991128435A Expired - Fee Related CN1133493C (en) | 1999-04-14 | 1999-04-14 | Efficient catalyst for synthesizing ammonia and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1133493C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299823C (en) * | 2004-10-10 | 2007-02-14 | 福州开发区科盛催化材料有限公司 | Methanation resisting active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity |
| CN100421788C (en) * | 2006-03-03 | 2008-10-01 | 厦门大学 | Mixed ruthenium base amino synthetic catalyst and its preparing method |
| CN100448530C (en) * | 2007-05-23 | 2009-01-07 | 浙江工业大学 | Composite oxide supported ruthenium-based ammonia synthesis catalyst and its preparation method |
| CN103420797A (en) * | 2012-05-21 | 2013-12-04 | 中国科学院大连化学物理研究所 | Method of low metal loading catalyst for preparing glycol from carbohydrate |
| CN103420796A (en) * | 2012-05-21 | 2013-12-04 | 中国科学院大连化学物理研究所 | Method of a high metal loading catalyst for preparing glycol from carbohydrate |
| CN108435166A (en) * | 2018-03-22 | 2018-08-24 | 福州大学 | A kind of preparation method of free from chloride active carbon loading ruthenium ammonia synthesis catalyst |
| CN114733551A (en) * | 2022-05-06 | 2022-07-12 | 福州大学 | High-performance Ru-based ammonia synthesis catalyst and preparation method and application thereof |
-
1999
- 1999-04-14 CN CNB991128435A patent/CN1133493C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299823C (en) * | 2004-10-10 | 2007-02-14 | 福州开发区科盛催化材料有限公司 | Methanation resisting active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity |
| CN100421788C (en) * | 2006-03-03 | 2008-10-01 | 厦门大学 | Mixed ruthenium base amino synthetic catalyst and its preparing method |
| CN100448530C (en) * | 2007-05-23 | 2009-01-07 | 浙江工业大学 | Composite oxide supported ruthenium-based ammonia synthesis catalyst and its preparation method |
| CN103420797A (en) * | 2012-05-21 | 2013-12-04 | 中国科学院大连化学物理研究所 | Method of low metal loading catalyst for preparing glycol from carbohydrate |
| CN103420796A (en) * | 2012-05-21 | 2013-12-04 | 中国科学院大连化学物理研究所 | Method of a high metal loading catalyst for preparing glycol from carbohydrate |
| CN103420797B (en) * | 2012-05-21 | 2015-04-08 | 中国科学院大连化学物理研究所 | Method of low metal loading catalyst for preparing glycol from carbohydrate |
| CN103420796B (en) * | 2012-05-21 | 2015-05-20 | 中国科学院大连化学物理研究所 | Method of a high metal loading catalyst for preparing glycol from carbohydrate |
| CN108435166A (en) * | 2018-03-22 | 2018-08-24 | 福州大学 | A kind of preparation method of free from chloride active carbon loading ruthenium ammonia synthesis catalyst |
| CN114733551A (en) * | 2022-05-06 | 2022-07-12 | 福州大学 | High-performance Ru-based ammonia synthesis catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1133493C (en) | 2004-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1179788C (en) | Unsaturated hydrocarbon selective hydrogenation catalyst, its preparation process and use thereof | |
| CN1117618C (en) | Catalyst for production of ethylene oxide, method for production thereof, and method for production of ethylene oxide | |
| CN112280052B (en) | Hierarchical pore ZIF-8 material and preparation method and application thereof | |
| CN1017597B (en) | Process for production desulfurization agent | |
| CN1080585C (en) | Photocatalyst, method for preparing the same, and production of hydrogen using the same | |
| CN1548227A (en) | Catalyst for preparing carbon nanotube and its prepn | |
| CN1270081A (en) | Efficient catalyst for synthesizing ammonia and its preparing process | |
| CN114177940A (en) | Preparation and application of monoatomic Cu-anchored covalent organic framework material | |
| CN1416949A (en) | Metal oxide catalyst for synthesizing methyl carbonate by urea process and its prepn | |
| CN1401426A (en) | Ammonia synthesis ruthenium based catalyst and preparing process thereof | |
| CN1093433C (en) | Catalyst for self-heating oxidation and reforming of natural gas to produce synthetic gas and its preparation process | |
| CN1131101C (en) | Ru-based ammonia synthesizing catalyst carried by nano carbon fiber and its prepn. | |
| CN107376988B (en) | High-activity propylene gas-phase epoxidation catalyst, and preparation method and application thereof | |
| CN1176746C (en) | Fischer-Tropsch catalyst and its preparing process | |
| CN1506300A (en) | Ruthenium-based catalyst for decomposing ammonia to prepare mixed H2-N2 gas and its prepn | |
| CN1739852A (en) | Catalyst for preparing p-cyclodexanone dioxide | |
| CN1795987A (en) | Catalyst of Mo, V, Te, Nb in use for reaction of producing crylic acid by selective oxidation of propane | |
| CN1118325C (en) | Catalyst for synthesizing dimethyl carbonate and its application | |
| CN1218915C (en) | Solid acid catalyst for preparing ethylene glycol by ethylene oxide hydration | |
| CN1080589C (en) | Double metal cyanide catalyst and its prepn. method | |
| CN1310129A (en) | Zns photocatalyst, its producing method and method for producing hydrogen using with the same catalyst | |
| CN111939966A (en) | Alkaline molecular sieve catalyst, preparation method thereof and application thereof in synthesis of N-methylmorpholine oxide | |
| CN1015875B (en) | Catalytic agent for preparing isoprene by isobutylene-methanal gas phase condensation | |
| CN1150992C (en) | catalyzer utilized to synthesize oxalate and its preparation method | |
| CN1228239C (en) | Method preparing synthetic gas using oxygen carrying type lattice oxygen catalyst |
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 | ||
| 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 |