CN105457647A - Nano-perovskite-type catalyst La(1-X)BixCoO3 as well as preparation method and application thereof - Google Patents
Nano-perovskite-type catalyst La(1-X)BixCoO3 as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN105457647A CN105457647A CN201510910721.0A CN201510910721A CN105457647A CN 105457647 A CN105457647 A CN 105457647A CN 201510910721 A CN201510910721 A CN 201510910721A CN 105457647 A CN105457647 A CN 105457647A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- citric acid
- nitrate
- nano
- coo
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of chemical catalysts and particularly provides a ABO3 nano-perovskite-type catalyst La(1-X)BixCoO3 as well as a preparation method and an application thereof. Lanthanum nitrate, cobalt nitrate and bismuth nitrate are mixed with sucrose and citric acid, a solution is regulated to be neutral, then gel is formed and subjected to heat treatment in a nitrogen atmosphere, and the nano-perovskite-type catalyst La(1-X)BixCoO3 is prepared. The prepared catalyst has good activity and stability, can be used for purifying recycle gas in a glyoxal production process through air oxidation of ethylene glycol, specifically, the catalyst oxidizes organic matters in the air efficiently under the working condition of glyoxal production through air oxidation of ethylene glycol, and the recycle gas is purified.
Description
Technical field
The invention belongs to chemical catalyst technical field, be specifically related to a kind of nano-perovskite type catalyst La
1-Xbi
xcoO
3and its preparation method and application.
Background technology
Glyoxal has important purposes in numerous industries such as weaving, pharmacy, microelectronics, space flight, the production method of its main flow adopts adiabatic reactor reactor, ethylene glycol and air carry out the partial oxidation reaction of ethylene glycol on silver or silver-bearing copper catalyst at 400-600 DEG C, product water obtains the glyoxal water solution product that weight solubility is 40% after absorbing.The reaction that ethylene glycol moieties oxidation generates glyoxal is a strong exothermal reaction, in order to maintain stable reaction temperature, part nitrogen in reaction afterproduct gas will, as moving hot gas at system Inner eycle, therefore have circulating air to circulate in reaction system all the time in course of reaction.When ethylene glycol carries out air oxidation reaction, except generating glyoxal, also formaldehyde can be generated, acetaldehyde, glycollic aldehyde, formic acid, the accessory substances such as acetic acid, these volatile organic matters, in circulating air, have a strong impact on glyoxal product quality on the one hand, cause the discharge of waste water and waste gas on the other hand, bring very large pressure to environmental protection.Current reaction system carries out water scrubber washing to circulating air, but effect is very limited, if can by the organic matter removing in circulating air, by the environmental friendliness of the raising and production that contribute to product quality.
Ethylene glycol air oxidation produce in the circulating air of glyoxal containing have an appointment 6% oxygen, the content of volatile organic matter is hundreds of ppm, and in circulating air, directly utilize catalyst combustion reaction to be removed by the volatile organic matter such as formaldehyde is best bet.But because circulating air is at reaction unit Inner eycle, can not affect main reaction to the purification of circulating air, namely can not change the temperature of circulating air and improve oxygen content, this proposes high requirement to catalyst.Ethylene glycol air oxidation is produced containing a large amount of saturated steams in the circulating air of glyoxal, and the oxygen content in circulating air is lower again, and the common catalyst for volatile organic compounds by catalytic combustion does not almost have activity under this working condition.
Chinese patent ZL201010564984.8 reports a kind of La adopting combustion method of citric acid to prepare
1-Xbi
xcoO
3perovskite structure catalyst, catalysis methanol complete oxidation has showed high activity.A certain amount of lanthanum nitrate, cobalt nitrate and bismuth nitrate dilute nitric acid solution dissolve by this catalyst, are then that 1:1.1 adds citric acid according to the ratio of metal ion and citric acid, 70 after dissolving completely
0aeration-drying under C, then 600-700 in Muffle furnace
0c roasting obtains catalyst.The catalyst crystal grain obtained through high-temperature roasting is like this micron order, under higher oxygen concentration, just have high activity, is applicable to the removal of volatile organic matter in air.For the circulating air of glyoxal production technology, its oxygen content only has an appointment 6%, and catalyst disclosed in this patent is difficult to the volatile organic matter removed wherein, needs exploitation can have highly active catalyst under low oxygen content.
Summary of the invention
Order of the present invention is that providing a kind of has the efficient nano-perovskite type catalyst La removing volatile organic matter under low oxygen content
1-Xbi
xcoO
3and preparation method thereof, and be applied to the catalytic purification that circulating air in glyoxal technique is produced in ethylene glycol air oxidation.
Nano-perovskite type catalyst La provided by the invention
1-Xbi
xcoO
3preparation method, concrete steps are as follows:
(1) according to La
1-Xbi
xcoO
3in X value, 0.05<X<0.3, takes lanthanum nitrate, cobalt nitrate and bismuth nitrate in proportion, and red fuming nitric acid (RFNA), be dissolved in deionized water, be mixed with nitrate solution, wherein nitric acid, the mol ratio of metal ion and water is (1 ~ 2): (2 ~ 4): 70; Separately take citric acid and sucrose is dissolved in deionized water, be mixed with citric acid solution, wherein sucrose, the mol ratio of citric acid and water is (1 ~ 2): (4 ~ 8): 40;
(2) nitrate solution is heated to 70 ~ 80 DEG C, drip citric acid solution in this temperature with under stirring, the citric acid amount added and the mol ratio of metal ion are 1:1 ~ 1:2; Nitrate solution and citric acid solution fully mix rear concentrated ammonia liquor and adjust pH value of solution to 7; Keep obtaining gel after 2 ~ 3 hours at 75 ~ 80 DEG C;
(3) gained gel is dried into xerogel at 90 ~ 100 DEG C, then under nitrogen atmosphere 350 ~ 400 DEG C process 0.5 ~ 1 hour, obtain nano-perovskite catalyst La
1-Xbi
xcoO
3.
In above-mentioned preparation method, lanthanum element and bismuth element form perovskite ABO
3a position in structure, cobalt element forms B position: wherein 0.05<X<0.3.In catalyst, the ratio of lanthanum element and bismuth element sum, cobalt element and oxygen element mole is 1:1:3.
In above-mentioned preparation method, sucrose is at citric acid combustion process Zhong Youyige XianCheng carbon, and laggard oxidation step becomes the process of carbon dioxide, and this process can stablize La
1-Xbi
xcoO
3nanostructured.
In the sol-gel process that the present invention is used, citric acid, in xerogel calcination process, is a kind of fuel, serve as reducing agent, nitrate anion then serves as oxidant, and when nitrate radical content is lower, citric acid burning is not thorough, liberated heat is few, do not reach the heat needed for crystal growth, make product occur amorphous state, simultaneously, it is residual that nitrate anion quantity not sufficient makes sucrose become carbon, affects product purity and performance.Nitrate anion amount is excessive, and burning can be made too fast, and the crystal grain of generation is excessive.When the ratio of metal ion, citric acid, nitric acid, sucrose is suitable, just there is suitable burn rate, thus obtain nanocrystal.
In above-mentioned preparation method, the xerogel after oven dry under nitrogen atmosphere 350 ~ 400 DEG C process 0.5 ~ 1 hour, with this understanding, citric acid and sucrose can burnout and obtain nano level perovskite catalyst La
1-Xbi
xcoO
3.
Adopt the catalyst that said method prepares, can be used for ethylene glycol air oxidation and produce recycle gas purification in glyoxal technique, particularly, the oxygen in circulating air is directly utilized to carry out catalyst combustion reaction to volatile organic matters such as the formaldehyde in circulating air on a catalyst, thus reach the object of recycle gas purification, without the need to heating catalytic bed in addition or allocating air into, very economical and environmental friendliness.
Detailed description of the invention
Below by embodiment, the invention will be further elaborated:
Catalytic combustion reactor for decontamination cycle gas is arranged in the circulating air gas circuit of glyoxal production, and reactor installation site is before circulating air and the mixing of ethylene glycol raw material.Recycle gas purification Catalyst packing in the reactor, circulating air temperature 300-350 DEG C, circulating air air speed 1000h
-1.The performance of catalyst is expressed with the conversion ratio of organic matter complete oxidation in circulating air, and when conversion ratio reaches 100%, the organic matter in all circulating air is all oxidized to carbon dioxide.
Nano-perovskite type catalyst La
1-Xbi
xcoO
3the concrete steps of preparation are as follows:
(1) according to La
1-Xbi
xcoO
3in X value (be respectively X=0.05,0.10,0.15,0.20,0.25,0.30), title ratio gets a certain amount of lanthanum nitrate, cobalt nitrate and bismuth nitrate, be dissolved in a certain amount of deionized water with a certain amount of red fuming nitric acid (RFNA) and be made into nitrate solution, wherein nitric acid, the mol ratio of metal ion and water is 1:2:70.Separately get a certain amount of citric acid and sucrose to be dissolved in deionized water and to be made into citric acid solution, wherein sucrose, the mol ratio of citric acid and water is 1:4:40;
(2) nitrate solution is heated to 80 DEG C, drip citric acid solution in this temperature with under stirring, the citric acid amount added and the mol ratio of metal ion are 1:2.Nitrate solution and citric acid solution fully mix rear concentrated ammonia liquor and adjust pH value of solution to 7.Remain on 80 DEG C, after about 2 hours, obtain gel;
(3) gained gel is dried into xerogel at 100 DEG C, then under nitrogen atmosphere 350 DEG C process 0.5 hour, obtain nano-perovskite catalyst La respectively
0.95bi
0.05coO
3(catalyst A), La
0.9bi
0.1coO
3(catalyst B)
,la
0.85bi
0.15coO
3(catalyst C), La
0.8bi
0.2coO
3(catalyst D), La
0.75bi
0.25coO
3(catalyst E) and La
0.7bi
0.3coO
3(catalyst F).
Catalyst A-F is used for ethylene glycol air oxidation and produces the catalytic performance of recycle gas purification in glyoxal technique in table 1.
The reactivity worth of table 1 catalyst
。
Claims (4)
1. a nano-perovskite type catalyst La
1-Xbi
xcoO
3preparation method, it is characterized in that concrete steps are as follows:
(1) according to La
1-Xbi
xcoO
3in X value, 0.05<X<0.3, takes lanthanum nitrate, cobalt nitrate and bismuth nitrate in proportion, and red fuming nitric acid (RFNA), be dissolved in deionized water, be mixed with nitrate solution, wherein nitric acid, the mol ratio of metal ion and water is (1 ~ 2): (2 ~ 4): 70; Separately take citric acid and sucrose is dissolved in deionized water, be mixed with citric acid solution, wherein sucrose, the mol ratio of citric acid and water is (1 ~ 2): (4 ~ 8): 40;
(2) nitrate solution is heated to 70 ~ 80 DEG C, drip citric acid solution in this temperature with under stirring, the citric acid amount added and the mol ratio of metal ion are 1:1 ~ 1:2; Nitrate solution and citric acid solution fully mix rear concentrated ammonia liquor and adjust pH value of solution to 7; Keep obtaining gel after 2 ~ 3 hours at 75 ~ 80 DEG C;
(3) gained gel is dried into xerogel at 90 ~ 100 DEG C, then under nitrogen atmosphere 350 ~ 400 DEG C process 0.5 ~ 1 hour, obtain nano-perovskite catalyst La
1-Xbi
xcoO
3.
2. preparation method according to claim 1, is characterized in that the ratio of lanthanum element and bismuth element sum, cobalt element and oxygen element mole in catalyst is 1:1:3.
3. the nano-perovskite type catalyst La prepared by the described preparation method of one of claim 1-2
1-Xbi
xcoO
3.
4. nano-perovskite type catalyst La according to claim 3
1-Xbi
xcoO
3produce in glyoxal technique in ethylene glycol air oxidation and apply in recycle gas purification, it is characterized in that utilizing the oxygen in circulating air to carry out catalyst combustion reaction to volatile organic matters such as the formaldehyde in circulating air on a catalyst, thus make recycle gas purification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510910721.0A CN105457647B (en) | 2015-12-10 | 2015-12-10 | Nano perovskite type catalyst La1-XBiXCoO3And preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510910721.0A CN105457647B (en) | 2015-12-10 | 2015-12-10 | Nano perovskite type catalyst La1-XBiXCoO3And preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105457647A true CN105457647A (en) | 2016-04-06 |
| CN105457647B CN105457647B (en) | 2021-02-26 |
Family
ID=55596061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510910721.0A Active CN105457647B (en) | 2015-12-10 | 2015-12-10 | Nano perovskite type catalyst La1-XBiXCoO3And preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105457647B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108455902A (en) * | 2016-06-22 | 2018-08-28 | 金华知产婺源信息技术有限公司 | A kind of preparation method of the fire retardant man-made stone comprising nano-perovskite oxide |
| CN111054368A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Integral non-noble metal catalyst for processing oxidation tail gas of PTA device and application |
| CN111054355A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Integral non-noble metal catalyst for catalytic combustion treatment of PTA tail gas |
| CN111054352A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Integral non-noble metal catalyst for purifying PTA oxidized tail gas and preparation method thereof |
| CN114345124A (en) * | 2022-01-14 | 2022-04-15 | 黎新安 | Air purifying agent capable of rapidly degrading formaldehyde and preparation method thereof |
| CN116082130A (en) * | 2023-02-03 | 2023-05-09 | 杭州富阳永星化工有限公司 | Process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010011A (en) * | 2010-10-29 | 2011-04-13 | 北京工业大学 | New method for preparing polycrystalline SrFeO3 with three-dimensional ordered macroporous structure |
| CN102059046A (en) * | 2010-11-30 | 2011-05-18 | 复旦大学 | Method for catalyzing methanol to be completely oxidatively decomposed into CO2 and H2O |
| CN105080553A (en) * | 2015-08-04 | 2015-11-25 | 内蒙古大学 | Method for preparing stanniferous double-perovskite type phenol photocatalytic degradation catalyst |
-
2015
- 2015-12-10 CN CN201510910721.0A patent/CN105457647B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010011A (en) * | 2010-10-29 | 2011-04-13 | 北京工业大学 | New method for preparing polycrystalline SrFeO3 with three-dimensional ordered macroporous structure |
| CN102059046A (en) * | 2010-11-30 | 2011-05-18 | 复旦大学 | Method for catalyzing methanol to be completely oxidatively decomposed into CO2 and H2O |
| CN105080553A (en) * | 2015-08-04 | 2015-11-25 | 内蒙古大学 | Method for preparing stanniferous double-perovskite type phenol photocatalytic degradation catalyst |
Non-Patent Citations (1)
| Title |
|---|
| MRIDULA BISWAS: "Synthesis of single phase rhombohedral LaNiO3 at low temperature and its characterization", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108455902A (en) * | 2016-06-22 | 2018-08-28 | 金华知产婺源信息技术有限公司 | A kind of preparation method of the fire retardant man-made stone comprising nano-perovskite oxide |
| CN108455902B (en) * | 2016-06-22 | 2021-01-01 | 余笑眉 | Preparation method of flame-retardant artificial stone containing nano perovskite oxide |
| CN111054368A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Integral non-noble metal catalyst for processing oxidation tail gas of PTA device and application |
| CN111054355A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Integral non-noble metal catalyst for catalytic combustion treatment of PTA tail gas |
| CN111054352A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Integral non-noble metal catalyst for purifying PTA oxidized tail gas and preparation method thereof |
| CN111054368B (en) * | 2018-10-16 | 2022-07-12 | 中国石油化工股份有限公司 | Integral non-noble metal catalyst for processing oxidation tail gas of PTA device and application |
| CN111054355B (en) * | 2018-10-16 | 2022-10-11 | 中国石油化工股份有限公司 | Integral non-noble metal catalyst for catalytic combustion treatment of PTA tail gas |
| CN114345124A (en) * | 2022-01-14 | 2022-04-15 | 黎新安 | Air purifying agent capable of rapidly degrading formaldehyde and preparation method thereof |
| CN114345124B (en) * | 2022-01-14 | 2023-11-03 | 广东九田环保科技有限公司 | Air purifying agent capable of rapidly degrading formaldehyde and preparation method thereof |
| CN116082130A (en) * | 2023-02-03 | 2023-05-09 | 杭州富阳永星化工有限公司 | Process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver |
| CN116082130B (en) * | 2023-02-03 | 2024-03-29 | 杭州富阳永星化工有限公司 | Process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105457647B (en) | 2021-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105457647A (en) | Nano-perovskite-type catalyst La(1-X)BixCoO3 as well as preparation method and application thereof | |
| CN106215692B (en) | A kind of processing method of carbon based metal organic backbone type oxide catalyst denitrating flue gas | |
| CN103894182B (en) | A kind of have the catalyst for denitrating flue gas in wide active temperature interval and preparation method thereof | |
| CN105032395B (en) | Zirconium doping cerium vanadate denitrating catalyst, preparation method and application | |
| CN107649116A (en) | Cerium tin composite oxides denitrating catalyst and its preparation method and application | |
| CN102764645A (en) | SCR (selective catalytic reduction) nitrogen oxide catalyst, and preparation method and application thereof | |
| CN101804344A (en) | Manganese/carbon nanotube denitrification catalytic reduction catalyst and preparation method thereof | |
| CN105363451A (en) | Efficient catalyst for decomposition of N2O and preparation method and application thereof | |
| CN109821531B (en) | Cerium oxide carrier-based flat plate type high-temperature sulfur-resistant SCR denitration catalyst and preparation method thereof | |
| CN112844370A (en) | Vanadium-titanium catalyst and preparation method and application thereof | |
| CN111185191B (en) | Preparation method of micro-nickel regulated manganese oxide catalyst, product and application thereof | |
| CN113786828A (en) | Catalyst for synergistic removal of NOx and CVOCs and preparation method and application thereof | |
| CN108940302A (en) | A kind of O composite metallic oxide catalyst and its preparation method and application | |
| CN105289586A (en) | Spherical cerium-manganese composite oxide low-temperature denitration catalyst, and preparation method and application thereof | |
| CN106513005A (en) | A preparing method of an iron-based composite oxide catalyst | |
| CN107837800B (en) | Titanium dioxide catalytic ozonation catalyst, preparation and denitration application | |
| CN104566405A (en) | PTA (purified terephthalio acid) oxidized tail gas catalytic combustion processing method with low energy consumption | |
| CN106334573A (en) | Preparation method of catalyst for selectively catalyzing and reducing nitrogen oxide | |
| CN111282578B (en) | Metal-doped manganese-based low-temperature denitration catalyst and preparation method thereof | |
| CN105536805B (en) | Nano copper-cerium composite oxide catalyst and preparation method and application thereof | |
| CN113877568B (en) | Porous high-temperature-resistant catalyst and preparation method thereof | |
| CN112169808A (en) | Desulfurization and denitrification catalyst and preparation method thereof | |
| CN105289263A (en) | Hydrogen peroxide denitration process and denitration system | |
| CN103962134A (en) | Method for eliminating chloro aromatic hydrocarbon through low-temperature catalytic combustion | |
| CN106698616A (en) | Method for reduction preparation of silver loaded activated carbon from citric acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |