CN102962074B - Denitration catalyst of wide activity temperature window as well as preparation method and application thereof - Google Patents
Denitration catalyst of wide activity temperature window as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN102962074B CN102962074B CN201210469938.9A CN201210469938A CN102962074B CN 102962074 B CN102962074 B CN 102962074B CN 201210469938 A CN201210469938 A CN 201210469938A CN 102962074 B CN102962074 B CN 102962074B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- gained
- solution
- denitration catalyst
- 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.)
- Active
Links
Abstract
The invention provides a denitration catalyst of a wide activity temperature window as well as a preparation method and application of the denitration catalyst, and belongs to the technical fields of environment catalysis and atmosphere pollution control. The composite oxide catalyst is prepared by a hydrothermal method. The denitration catalyst is characterized in that the activity temperature window is wide and has good waterproof property and good sulfur tolerance. The provided method for reducing nitric oxide comprises the following steps of: loading the catalyst in a reactor of a stationary bed; controlling the reaction temperature within the range of 150-400 DEG C; and using ammonia as a reducing agent. According to the copper-cerium-titanium composite oxide prepared by the invention, the air speed is 64000/h; and the purification efficiency of the nitric oxide is 91-99% within the range of 200-400 DEG C.
Description
Technical field
A kind of method that the present invention relates to composite oxide catalysts and preparation thereof and utilize this catalyst selective catalyst reduction of nitrogen oxides under excess oxygen.Be applicable to the mobile former discharge nitrogen oxide (NO such as the stationary sources such as coal-burning power plant, Industrial Boiler, calcining kiln and lean-burn gasoline motor car and diesel vehicle
x) elimination, belong to environmental catalysis and air pollution control technique field.
Background technology
Along with the growth of energy-consuming and the increase of vehicle guaranteeding organic quantity, a large amount of Fossil fuel consumptions, nitrogen oxide emission constantly increases, and the problems such as its acid rain causing, photochemical fog have become the global environmental problem becoming increasingly conspicuous, therefore, NO
xemission control become the focus of a research in current atmosphere environmental technology field.
Ammonia SCR (Selective catalytic reduction, SCR) is considered to stationary source tail flue gas NO
xone of effective method of pollute controlling.The key of SCR technology is the catalyst of efficient stable.At present, the NH of industrial applications
3-SCR catalyst is mainly V
2o
5-WO
3/ TiO
2catalyst, this catalyst has good catalytic performance within the scope of 320-400 ℃.But the problem that this catalyst exists is active constituent V
2o
5precursor toxicity large, easily cause environmental pollution; And when flue-gas temperature is during lower than 300 ℃, the denitration performance of catalyst is low.And the smog discharge temperature of boiler of power plant changes with load, even if temperature during underrun before air preheater also may be down to below 250 ℃.Domestic and international existing SCR catalyst can not be applied to the flue gas condition of boiler of power plant underrun.In addition, there is a large amount of industrial combustion equipments in China, comprise Industrial Boiler, calcining kiln and cement rotary kiln etc., in flue-gas temperature between air preheater and economizer conventionally between 250-350 ℃, lower than coal-fired power station boiler flue-gas temperature (320-400 ℃), therefore, the denitrating catalyst of exploitation wide temperature window, can not only meet the NO under different load condition of power plant
xelimination, also simultaneously can meet the technical need of China's industrial combustion equipment denitrating flue gas, have great importance and application prospect.
The present invention by hydro-thermal method prepared a kind of in wide temperature range to NO
xremove well behaved NEW TYPE OF COMPOSITE oxide catalyst.
Summary of the invention
The object of this invention is to provide a kind of preparation technology simple and to ammonia selective reducing NO
xthere is high efficiency composite oxide catalysts and preparation method thereof.Concerted catalysis effect in performance copper cerium-titanium composite oxide between each component, improves the performance of catalyst, thus made a kind of environmental friendliness and in wide temperature range to NO
xwell behaved denitrating catalyst is eliminated in catalysis.
The object of the invention is to be achieved through the following technical solutions:
The denitrating catalyst of wide active temperature windows, is characterized in that: raw material composition is expressed as Cu
xce
yti
1-x-yo
2, molar content 0.1≤x≤0.3 of Cu wherein, molar content 0.1≤y≤0.3 of Ce, the molar content of Ti is between 0.4-0.8.
The preparation method of the denitrating catalyst of described wide active temperature windows, is characterized in that: the method comprises the following steps successively:
(1) copper nitrate and the cerous nitrate solution of preparation 0.5 ~ 1.0mol/L, the titanium sulfate solution of 1 ~ 2 mol/L;
(2) get step (1) gained copper nitrate, cerous nitrate and titanium sulfate solution, 30 ~ 50 ℃ of stirring in water bath are mixed 30 ~ 90 minutes, obtain mixed solution;
(3) step (2) gained mixed solution being added to ammoniacal liquor to pH value under constantly stirring is 10, and gained mixed liquor is transferred in hydrothermal reaction kettle, 120 ℃ of condition hydro-thermal reactions 12 ~ 24 hours, is then down to room temperature;
(4) get step (3) gained reactant liquor suction filtration, washing is dried 12 ~ 48 hours under 120 ℃ of conditions, and then roasting 4 ~ 8 hours under 500 ℃ of conditions in Muffle furnace makes the denitrating catalyst of wide active temperature windows.
The application of the denitrating catalyst of described wide active temperature windows, is characterized in that, this application process comprises the following steps:
By catalyst loading, in the middle of fixed bed reactors, reaction temperature is controlled at 150 ~ 400 ℃ of scopes; Take ammonia as reducing agent, control total gas flow rate at 200 ~ 400 ml/min, air speed is 64,000 ~ 128,000 h
-1.
The present invention compared with prior art, has the following advantages and high-lighting effect: do not adopt virose active component V
2o
5, by the concerted catalysis effect between performance copper cerium titanium component, effectively improved the low-temperature denitration performance of catalyst, widened the active temperature windows of catalyst, the performance that has possessed efficient catalytic purifying nitrogen oxide, within the scope of 200 ~ 400 ℃, the purification efficiency of nitrogen oxide reaches 91 ~ 99%.
The specific embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further:
Embodiment 1:Cu
0.1ce
0.1ti
0.8o
2the preparation of composite oxide catalysts
A) get respectively the titanium sulfate solution of the copper nitrate solution of 7.53ml 0.50 mol/L, the cerous nitrate solution of 7.49 ml 0.50 mol/L and 15.03 ml 2 mol/L, 30 ℃ of stirring in water bath are mixed 30 minutes, obtain mixed solution;
B) by step a) gained mixed solution under constantly stirring, to add ammoniacal liquor to pH value be 10, gained mixed liquor is transferred in hydrothermal reaction kettle, 120 ℃ of condition hydro-thermal reactions 24 hours, be then down to room temperature;
C) get step b) gained reactant liquor suction filtration, washing is dried 12 hours under 120 ℃ of conditions, and then roasting 6 hours under 500 ℃ of conditions in Muffle furnace, makes copper cerium and titanium compound oxide catalyst.
Embodiment 2:Cu
0.1ce
0.3ti
0.6o
2the preparation of composite oxide catalysts
A) get respectively the titanium sulfate solution of the copper nitrate solution of 3.77 ml 1.0 mol/L, the cerous nitrate solution of 11.31 ml 1.0 mol/L and 22.62 ml 1.0 mol/L, 50 ℃ of stirring in water bath are mixed 90 minutes, obtain mixed solution;
B) by step a) gained mixed solution under constantly stirring, to add ammoniacal liquor to pH value be 10, gained mixed liquor is transferred in hydrothermal reaction kettle, 120 ℃ of condition hydro-thermal reactions 12 hours, be then down to room temperature;
C) get step b) gained reactant liquor suction filtration, washing is dried 24 hours under 120 ℃ of conditions, and then roasting 4 hours under 500 ℃ of conditions in Muffle furnace, makes copper cerium and titanium compound oxide catalyst.
Embodiment 3:Cu
0.2ce
0.2ti
0.6o
2the preparation of composite oxide catalysts
A) get respectively the titanium sulfate solution of the copper nitrate solution of 7.53ml 1.0 mol/L, the cerous nitrate solution of 7.49 ml 1.0 mol/L and 11.27 ml 2 mol/L, 30 ℃ of stirring in water bath are mixed 60 minutes, obtain mixed solution;
B) by step a) gained mixed solution under constantly stirring, to add ammoniacal liquor to pH value be 10, gained mixed liquor is transferred in hydrothermal reaction kettle, 120 ℃ of condition hydro-thermal reactions 24 hours, be then down to room temperature;
C) get step b) gained reactant liquor suction filtration, washing is dried 48 hours under 120 ℃ of conditions, and then roasting 8 hours under 500 ℃ of conditions in Muffle furnace, makes copper cerium and titanium compound oxide catalyst.
Embodiment 4:Cu
0.3ce
0.1ti
0.6o
2the preparation of composite oxide catalysts
A) get respectively the titanium sulfate solution of the copper nitrate solution of 11.25 ml 1.0 mol/L, the cerous nitrate solution of 3.75 ml 1.0 mol/L and 11.25 ml 2 mol/L, 30 ℃ of stirring in water bath are mixed 60 minutes, obtain mixed solution;
B) by step a) gained mixed solution under constantly stirring, to add ammoniacal liquor to pH value be 10, gained mixed liquor is transferred in hydrothermal reaction kettle, 120 ℃ of condition hydro-thermal reactions 24 hours, be then down to room temperature;
C) get step b) gained reactant liquor suction filtration, washing is dried 24 hours under 120 ℃ of conditions, and then roasting 4 hours under 500 ℃ of conditions in Muffle furnace, makes copper cerium and titanium compound oxide catalyst.
Embodiment 5:Cu
0.3ce
0.3ti
0.4o
2the preparation of composite oxide catalysts
A) get respectively the titanium sulfate solution of the copper nitrate solution of 11.25ml 1.0 mol/L, the cerous nitrate solution of 11.25 ml 1.0 mol/L and 7.50 ml 2 mol/L, 30 ℃ of stirring in water bath are mixed 60 minutes, obtain mixed solution;
B) by step a) gained mixed solution under constantly stirring, to add ammoniacal liquor to pH value be 10, gained mixed liquor is transferred in hydrothermal reaction kettle, 120 ℃ of condition hydro-thermal reactions 24 hours, be then down to room temperature;
C) get step b) gained reactant liquor suction filtration, washing is dried 48 hours under 120 ℃ of conditions, and then roasting 8 hours under 500 ℃ of conditions in Muffle furnace, makes copper cerium and titanium compound oxide catalyst.
Embodiment 6(reference): Cu
0.1ti
0.9o
2the preparation of catalyst
A) get the titanium sulfate solution of 7.53ml 0.50 mol/L copper nitrate solution and 16.91ml 2.0 mol/L, 40 ℃ of stirring in water bath mix, and obtain mixed solution;
B) by step a) gained mixed solution under constantly stirring, to add ammoniacal liquor to pH value be 10, gained mixed liquor is transferred in hydrothermal reaction kettle, 120 ℃ of condition hydro-thermal reactions 24 hours, be then down to room temperature;
C) get step b) gained reactant liquor suction filtration, washing is dried 48 hours under 120 ℃ of conditions, and then roasting 6 hours under 500 ℃ of conditions in Muffle furnace, makes copper titanium compound oxide catalyst.
Embodiment 7(reference): Ce
0.1ti
0.9o
2the preparation of catalyst
A) get the titanium sulfate solution of 7.49 ml 0.50 mol/L cerous nitrate solutions and 16.91ml 2.0 mol/L, 40 ℃ of stirring in water bath mix, and obtain mixed solution;
B) by step a) gained mixed solution under constantly stirring, to add ammoniacal liquor to pH value be 10, gained mixed liquor is transferred in hydrothermal reaction kettle, 120 ℃ of condition hydro-thermal reactions 24 hours, be then down to room temperature;
C) get step b) gained reactant liquor suction filtration, washing is dried 48 hours under 120 ℃ of conditions, and then roasting 6 hours under 500 ℃ of conditions in Muffle furnace, makes cerium and titanium compound oxide catalyst.
Embodiment 8: the preparation method of catalyst is identical with embodiment 1, and 0.12 gram of catalyst is placed in to continuous fixed bed reactor, and reaction gas consists of 0.05% NO, 0.05% NH
3, 5% O
2, with nitrogen, do Balance Air, the flow velocity of reaction gas is 300 ml/min, air speed is 64,000 h
-1.Activity rating temperature range is 150-400 ℃, under different temperatures, and catalyst reduction NO
xconversion ratio in Table 1.
Embodiment 9: the preparation method of catalyst is identical with embodiment 2, and 0.12 gram of catalyst is placed in to continuous fixed bed reactor, and reaction gas consists of 0.05% NO, 0.05% NH
3, 5% O
2, with nitrogen, do Balance Air, the flow velocity of reaction gas is 300 ml/min, air speed is 64,000 h
-1.Activity rating temperature range is 150-400 ℃, under different temperatures, and catalyst reduction NO
xconversion ratio in Table 1.
Embodiment 10: the preparation method of catalyst is identical with embodiment 3, and 0.12 gram of catalyst is placed in to continuous fixed bed reactor, and reaction gas consists of 0.05% NO, 0.05% NH
3, 5% O
2, with nitrogen, do Balance Air, the flow velocity of reaction gas is 300 ml/min, air speed is 64,000 h
-1.Activity rating temperature range is 150-400 ℃, under different temperatures, and catalyst reduction NO
xconversion ratio in Table 1.
Embodiment 11: the preparation method of catalyst is identical with embodiment 4, and 0.12 gram of catalyst is placed in to continuous fixed bed reactor, and reaction gas consists of 0.05% NO, 0.05% NH
3, 5% O
2, with nitrogen, do Balance Air, the flow velocity of reaction gas is 300 ml/min, air speed is 64,000 h
-1.Activity rating temperature range is 150-400 ℃, under different temperatures, and catalyst reduction NO
xconversion ratio in Table 1.
Embodiment 12: the preparation method of catalyst is identical with embodiment 5, and 0.12 gram of catalyst is placed in to continuous fixed bed reactor, and reaction gas consists of 0.05% NO, 0.05% NH
3, 5% O
2, with nitrogen, do Balance Air, the flow velocity of reaction gas is 300 ml/min, air speed is 64,000 h
-1.Activity rating temperature range is 150-400 ℃, under different temperatures, and catalyst reduction NO
xconversion ratio in Table 1.
Table 1 copper titanium, cerium titanium and copper cerium titanium catalyst activity rating result
Embodiment 13: the preparation method of catalyst is identical with embodiment 1, and 0.12 gram of catalyst is placed in to continuous fixed bed reactor, and reaction gas consists of 0.05% NO, 0.05% NH
3, 5% O
2, 5% H
2o, 50ppm SO
2, with nitrogen, do Balance Air, the flow velocity of reaction gas is 300 ml/min, air speed is 64,000 h
-1.Activity rating temperature range is 150-400 ℃, under different temperatures, and catalyst reduction NO
xconversion ratio in Table 2.
Embodiment 14: the preparation method of catalyst is identical with embodiment 2, and 0.12 gram of catalyst is placed in to continuous fixed bed reactor, and reaction gas consists of 0.05% NO, 0.05% NH
3, 5% O
2, 5% H
2o, 50ppm SO
2, with nitrogen, do Balance Air, the flow velocity of reaction gas is 300 ml/min, air speed is 64,000 h
-1.Activity rating temperature range is 150-400 ℃, under different temperatures, and catalyst reduction NO
xconversion ratio in Table 2.
Table 2 copper titanium, cerium titanium and copper cerium titanium catalyst are at water and SO
2activity rating result while coexisting
Claims (2)
1. the denitrating catalyst of wide active temperature windows, is characterized in that: raw material composition is expressed as Cu
xce
yti
1-x-yo
2, molar content 0.1≤x≤0.3 of Cu wherein, molar content 0.1≤y≤0.3 of Ce, the molar content of Ti is between 0.4-0.8, and preparation method comprises the following steps successively:
(1) copper nitrate and the cerous nitrate solution of preparation 0.5～1.0mol/L, the titanium sulfate solution of 1～2mol/L;
(2) get step (1) gained copper nitrate, cerous nitrate and titanium sulfate solution, 30～50 ℃ of stirring in water bath are mixed 30～90 minutes, obtain mixed solution;
(3) step (2) gained mixed solution being added to ammoniacal liquor to pH value under constantly stirring is 10, and gained mixed liquor is transferred in hydrothermal reaction kettle, 120 ℃ of condition hydro-thermal reactions 12～24 hours, is then down to room temperature;
(4) get step (3) gained reactant liquor suction filtration, washing is dried 12～48 hours under 120 ℃ of conditions, and then roasting 4～8 hours under 500 ℃ of conditions in Muffle furnace makes the denitrating catalyst of wide active temperature windows.
2. the application of the denitrating catalyst of wide active temperature windows as claimed in claim 1, is characterized in that, this application process comprises the following steps:
(1) by catalyst loading in the middle of fixed bed reactors, reaction temperature is controlled at 150～400 ℃ of scopes;
(2) take ammonia as reducing agent, control total gas flow rate at 200～400ml/min, air speed is at 64,000～128,000h
-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210469938.9A CN102962074B (en) | 2012-11-19 | 2012-11-19 | Denitration catalyst of wide activity temperature window as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210469938.9A CN102962074B (en) | 2012-11-19 | 2012-11-19 | Denitration catalyst of wide activity temperature window as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102962074A CN102962074A (en) | 2013-03-13 |
| CN102962074B true CN102962074B (en) | 2014-11-26 |
Family
ID=47792677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210469938.9A Active CN102962074B (en) | 2012-11-19 | 2012-11-19 | Denitration catalyst of wide activity temperature window as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102962074B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103433040B (en) * | 2013-08-29 | 2015-05-13 | 天津大学 | Binary metal modified titanium dioxide catalyst, preparation method thereof and application of catalyst in removal of nitric oxide contained in tail gas of diesel engine |
| CN105688888A (en) * | 2016-01-14 | 2016-06-22 | 济南大学 | High-performance vanadium, cerium and titanium composite oxide catalyst for flue gas denitration and preparation method thereof |
| CN107519945A (en) * | 2017-06-08 | 2017-12-29 | 河北威达蓝海环保科技有限公司 | A kind of handling process of wide temperature range denitrating catalyst raw material |
| CN108554462A (en) * | 2018-05-14 | 2018-09-21 | 南京工业大学 | A kind of cerium tungsten titanium denitrating catalyst and its preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101204650A (en) * | 2006-12-20 | 2008-06-25 | 中国科学院生态环境研究中心 | Cerium and titanium compound oxide catalyst for flue gases denitration |
| CN101327952A (en) * | 2008-07-24 | 2008-12-24 | 浙江大学 | Preparation of Ce4Ti9O24 composite oxides |
| CN101829573A (en) * | 2010-04-16 | 2010-09-15 | 环境保护部华南环境科学研究所 | Composite oxidant SCR (Selective Catalytic Reduction) denitrating catalyst, preparation method and applications thereof |
| CN102658161A (en) * | 2012-04-18 | 2012-09-12 | 山东大学 | Supported iron-based composite oxide catalyst and preparation method thereof |
| CN102909004A (en) * | 2012-11-04 | 2013-02-06 | 北京化工大学 | Compounded denitration catalyst, as well as preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080085231A1 (en) * | 2006-10-05 | 2008-04-10 | Frederic Vitse | System and method for reducing nitrogen oxides emissions |
-
2012
- 2012-11-19 CN CN201210469938.9A patent/CN102962074B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101204650A (en) * | 2006-12-20 | 2008-06-25 | 中国科学院生态环境研究中心 | Cerium and titanium compound oxide catalyst for flue gases denitration |
| CN101327952A (en) * | 2008-07-24 | 2008-12-24 | 浙江大学 | Preparation of Ce4Ti9O24 composite oxides |
| CN101829573A (en) * | 2010-04-16 | 2010-09-15 | 环境保护部华南环境科学研究所 | Composite oxidant SCR (Selective Catalytic Reduction) denitrating catalyst, preparation method and applications thereof |
| CN102658161A (en) * | 2012-04-18 | 2012-09-12 | 山东大学 | Supported iron-based composite oxide catalyst and preparation method thereof |
| CN102909004A (en) * | 2012-11-04 | 2013-02-06 | 北京化工大学 | Compounded denitration catalyst, as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102962074A (en) | 2013-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103769083B (en) | A kind of NO_x Reduction by Effective composite oxide catalysts and its preparation method and application | |
| CN103008002B (en) | Preparation method and application of Fe and Cu composite molecular sieve catalyst | |
| CN102909004B (en) | Compounded denitration catalyst, as well as preparation method and application thereof | |
| CN102989467B (en) | A kind of titania oxide supported type ferric vandate catalyst, preparation method and its usage | |
| CN102000560B (en) | Cerium-based composite oxide catalyst for catalyzing and purifying nitric oxide | |
| CN102029178B (en) | Copper-based molecular sieve catalyst and preparation method thereof | |
| CN102626653B (en) | Preparation method of SAPO-18-carried Cu-Fe catalyst for ammonia-selective catalytic elimination of NOx | |
| CN107552043B (en) | Supported low-temperature SCR denitration catalyst and preparation method thereof | |
| CN101879452B (en) | Manganese-based low-temperature denitration catalyst and preparation method thereof | |
| CN102614910A (en) | Ammonia-selective preparation method of SAPO-34 supported Cu-Fe catalyst for catalytically removing NOx | |
| CN110947377B (en) | Cerium-tin-based composite oxide catalyst for catalytic purification of nitrogen oxides, preparation method and application thereof | |
| CN108993476B (en) | Metal oxide-vanadate/TiO2Catalyst, preparation method and application thereof | |
| CN101554589B (en) | Copper and iron modified titanium dioxide pillared bentonite catalyst and preparation method thereof | |
| CN102553572A (en) | Selective catalytic reduction (SCR) catalyst of wide active temperature window and preparation method thereof | |
| CN103433033A (en) | Low-temperature denitration catalyst MnOx-CeO2-TiO2-Al2O3, and preparation method and application thereof | |
| CN102909003A (en) | Cerium vanadium titanium catalyst for catalytic reduction of nitrogen oxide and preparation method and application of cerium vanadium titanium catalyst | |
| CN102962074B (en) | Denitration catalyst of wide activity temperature window as well as preparation method and application thereof | |
| CN103816891B (en) | Cerium-molybdenum-zirconium composite oxide catalyst, and preparation method and application thereof | |
| CN103962126A (en) | Catalyst for selectively catalyzing and reducing nitrogen oxides and preparation method thereof | |
| CN103801325A (en) | Co-precipitation preparation method of composite oxide denitration catalyst | |
| CN105170174A (en) | Nitriding carbon-based catalyst used for low temperature SCR denitration and preparation method thereof | |
| CN108236956A (en) | A kind of preparation method of iron cerium titanium oxide catalyst | |
| CN109745995B (en) | Wide-temperature-window SCR flue gas denitration catalyst and preparation method and application thereof | |
| CN103055889A (en) | Low-temperature denitration MnOx-CuO-TiO2 catalyst as well as preparation method and application thereof | |
| CN108579731A (en) | A kind of preparation method of low-temperature denitration carbon-supported 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 |