CN112516998B - Volatile organic pollution gas purification catalyst and preparation method and application thereof - Google Patents

Volatile organic pollution gas purification catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN112516998B
CN112516998B CN202011495148.9A CN202011495148A CN112516998B CN 112516998 B CN112516998 B CN 112516998B CN 202011495148 A CN202011495148 A CN 202011495148A CN 112516998 B CN112516998 B CN 112516998B
Authority
CN
China
Prior art keywords
catalyst
volatile organic
preparation
solutions
gas purification
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
Application number
CN202011495148.9A
Other languages
Chinese (zh)
Other versions
CN112516998A (en
Inventor
余林
刘琪
程高
孙明
余伟雄
唐诗昌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong University of Technology
Original Assignee
Guangdong University of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Guangdong University of Technology filed Critical Guangdong University of Technology
Priority to CN202011495148.9A priority Critical patent/CN112516998B/en
Publication of CN112516998A publication Critical patent/CN112516998A/en
Application granted granted Critical
Publication of CN112516998B publication Critical patent/CN112516998B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to the field of material synthesis, and discloses a volatile organic pollutant gas purification catalyst, and a preparation method and application thereof. The preparation method comprises the following steps: respectively preparing manganese salt and alkali into solutions, mixing the two solutions, adding deionized water, reacting under an ultrasonic condition, centrifuging, washing and drying the obtained product to obtain the volatile organic pollutant gas purification catalyst. The method does not need to use additional template agent or surfactant, and has the advantages of simple operation, convenient control, low cost, low reaction temperature and high purification efficiency of the volatile organic pollution gas. Prepared porous Mn 3 O 4 The catalyst has large specific surface area and good low-temperature activity, can be applied to catalytic purification of volatile organic pollution gas in air, and has important significance for air purification.

Description

Volatile organic pollution gas purification catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of material synthesis, and particularly relates to a volatile organic pollutant gas purification catalyst, and a preparation method and application thereof.
Background
With the rapid development of industrialization and urbanization, the air quality problem is more and more important. Volatile organic pollutants (VOCs) are one of the main sources of atmospheric pollution, and the discharge of VOCs not only produces photochemical pollution, but also causes ozone layer destruction, animal and plant poisoning and other effects. Catalytic combustion reactions are one of the effective ways to purify VOCs. Therefore, the research and development of the high-efficiency and low-cost catalyst have important significance for the purification of VOCs. At present, the commonly used noble metal catalysts (gold, platinum, palladium and the like) have higher activity in the aspect of catalyzing and burning VOCs, but have the advantages of less resources, high price and easy poisoning. The transition metal oxide catalyst has the advantages of more resources, low price and good catalytic activity, thereby receiving extensive attention and research.
The porous material has the advantages of large specific surface area, developed pore structure and the like. Among the transition metal components, oxides of manganese are the usual ones. The manganese oxide has low price and good thermal stability, has variable price (+ 2, +3, + 4), shows good performance in catalytic combustion of VOCs, and has wide application prospect. The currently common preparation method of the mesoporous manganese oxide is mainly a template method, and a template agent, such as mesoporous silica, a surfactant and the like, is required to be used. And Mn 3 O 4 The application in catalytic combustion of VOCs is rare, most Mn 3 O 4 The preparation of the catalyst needs to be carried out through high-energy-consumption processes such as hydrothermal process or roasting process.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention mainly aims to provide a preparation method of a volatile organic pollutant gas purification catalyst.
The invention also aims to provide the volatile organic pollutant gas purification catalyst prepared by the preparation method.
The invention also aims to provide application of the volatile organic pollutant gas purification catalyst.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a volatile organic pollution gas purification catalyst comprises the following operation steps: respectively preparing manganese salt and alkali into solutions, mixing the two solutions, adding deionized water, reacting under an ultrasonic condition, centrifuging, washing and drying the obtained product to obtain the volatile organic pollutant gas purification catalyst.
The manganese salt is prepared into a solution with the molar concentration of 0.4-1.2 mol/L; the alkali is prepared into a solution with the molar concentration of 0.4-1.2 mol/L.
The manganese salt is manganese chloride, manganese nitrate, manganese sulfate or manganese acetate.
The solvent used for preparing the solution is ethanol, glycol, glycerol or acetone.
The volume ratio of the deionized water to the alkali prepared solution is 1.
The reaction time is 10-60min.
The volatile organic pollution gas purifying catalyst prepared by the preparation method.
The catalyst is applied to the purification of volatile organic pollution gas.
The principle of the present invention is to make trimanganese tetroxide precipitate together with byproducts (such as potassium chloride, potassium nitrate, sodium chloride, etc.) by using the property of low solubility of the byproducts in solutions (such as ethanol, ethylene glycol, etc.), at which time the byproducts act as templating agents, and then wash the byproducts away with water, thereby preparing a product having a porous structure. The method uses easily removable by-products as templating agents to prepare catalysts having porous structures. In addition, the particle size of the catalyst can be regulated by using ultrasonic conditions. The pore diameter can be adjusted and controlled by adjusting the dosage of the deionized water.
Compared with the prior art, the invention has the following advantages and effects:
(1) The method does not need to use additional template agent or surfactant, and has the advantages of simple operation, convenient control, low cost, low reaction temperature and high purification efficiency of the volatile organic pollution gas. .
(2) The Mn prepared by the invention has high specific surface area and is porous 3 O 4 Catalyst with pore size distribution of 10-80 nm and specific surface area of 70-150 m 2 (ii)/g; the catalyst has good low-temperature activity, can be applied to catalytic purification of volatile organic pollution gas in air, and has important significance for air purification.
Drawings
FIG. 1 is a schematic representation of porous Mn prepared according to the present invention 3 O 4 X-ray diffraction pattern of the catalyst.
FIG. 2 shows porous Mn prepared according to the present invention 3 O 4 Field emission scanning electron micrographs of the catalyst.
FIG. 3 shows porous Mn prepared by the present invention 3 O 4 Catalytic combustion toluene performance diagram of the catalyst.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the embodiments in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
The reagents used in the following examples, unless otherwise specified, were of analytical grade.
Example 1:
respectively preparing 0.4mol/L ethanol solution and 0.8mol/L ethanol solution from manganese chloride and potassium hydroxide, mixing the two solutions, adding 5mL deionized water, reacting for 30min under ultrasonic condition, centrifuging, washing with water, and drying to obtain porous Mn 3 O 4 A catalyst. The obtained catalyst was analyzed by X-ray diffraction and field emission scanning electron microscopy, and the results are shown in fig. 1 and 2, respectively.
Example 2:
the catalyst of this example was prepared essentially as in example 1, except that: the concentration of potassium hydroxide was 1.0mol/L, and the obtained catalyst was analyzed by X-ray diffraction, and the results were the same as in example 1.
Example 3:
the catalyst of this example was prepared essentially as in example 1, except that: the concentration of potassium hydroxide was 1.2mol/L, and the obtained catalyst was analyzed by X-ray diffraction, and the results were the same as in example 1.
Example 4:
the catalyst of this example was prepared essentially as in example 1, except that: the concentration of potassium hydroxide was 0.4mol/L, and the obtained catalyst was analyzed by X-ray diffraction, and the results were the same as in example 1.
Example 5:
the catalyst of this example was prepared essentially as in example 1, except that: the concentration of manganese chloride was 1.0mol/L, and the obtained catalyst was analyzed by X-ray diffraction, and the results thereof were the same as in example 1.
Example 6:
the catalyst of this example was prepared in substantially the same manner as in example 1, except that: the concentration of manganese chloride was 0.4mol/L, and the obtained catalyst was analyzed by X-ray diffraction, and the results were the same as in example 1.
Example 7:
the catalyst of this example was prepared essentially as in example 1, except that: an amount of deionized water was added of 1mL, and the obtained catalyst was analyzed by X-ray diffraction, and the result was the same as in example 1.
Example 8:
the catalyst of this example was prepared essentially as in example 1, except that: an amount of deionized water was added to the reaction mixture in an amount of 3mL, and the obtained catalyst was analyzed by X-ray diffraction, and the results thereof were the same as in example 1.
Example 9:
the catalyst of this example was prepared essentially as in example 1, except that: an amount of deionized water was added of 8mL, and the obtained catalyst was analyzed by X-ray diffraction, and the result was the same as in example 1.
Example 10:
the catalyst of this example was prepared essentially as in example 1, except that: an amount of deionized water was added of 10mL, and the obtained catalyst was analyzed by X-ray diffraction, and the result was the same as in example 1.
Example 11:
the catalyst of this example was prepared essentially as in example 1, except that: the ultrasonic reaction time was 10min, and the obtained catalyst was analyzed by X-ray diffraction, and the result was the same as in example 1.
Example 12:
the catalyst of this example was prepared essentially as in example 1, except that: the ultrasonic reaction time was 60min, and the obtained catalyst was analyzed by X-ray diffraction, and the results were the same as in example 1.
Example 13:
and testing the conversion rate of the catalyst to toluene by adopting a fixed bed reactor evaluation device. A quartz tube fixed bed reactor having an inner diameter of 8mm was charged with 0.1g of the catalyst obtained in example 1 above and 40 to 60 mesh, and an equal amount of quartz sand was mixed therein, and fed with toluene at a concentration of normal pressure1000ppm, space velocity of 20000h -1 (ii) a After the reaction is stable, the reaction raw materials and products are subjected to on-line chromatographic analysis. The activity pattern of the catalyst prepared in example 1 is shown in FIG. 3, which shows the catalytic combustion toluene performance of the catalyst, T 10 =182 ℃ (temperature required for toluene conversion to 10%), T 90 =212 ℃ (required temperature for toluene conversion to 90%), indicating that the catalyst of the invention is at large reaction space velocity (20000 h) -1 ) And the catalyst shows good toluene catalytic combustion activity in a low and wide reaction temperature range.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (3)

1. Porous Mn of volatile organic pollution gas purification catalyst 3 O 4 The preparation method is characterized by comprising the following operation steps: respectively preparing manganese chloride and potassium hydroxide into solutions, wherein ethanol is used as a solvent for preparing the solutions, the two solutions are mixed and then added with deionized water, and the volume ratio of the deionized water to the solution prepared from the potassium hydroxide is 1-1:2; reacting under ultrasonic condition, centrifuging, washing and drying the obtained product to obtain the porous Mn 3 O 4 Wherein the byproduct potassium chloride plays the role of a template agent, and a product with a porous structure is obtained after washing.
2. The production method according to claim 1, characterized in that: the manganese chloride is prepared into a solution with the molar concentration of 0.4-1.2 mol/L; the potassium hydroxide is prepared into a solution with the molar concentration of 0.4-1.2 mol/L.
3. The method of claim 1, wherein: the reaction time is 10-60min.
CN202011495148.9A 2020-12-17 2020-12-17 Volatile organic pollution gas purification catalyst and preparation method and application thereof Active CN112516998B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011495148.9A CN112516998B (en) 2020-12-17 2020-12-17 Volatile organic pollution gas purification catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011495148.9A CN112516998B (en) 2020-12-17 2020-12-17 Volatile organic pollution gas purification catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112516998A CN112516998A (en) 2021-03-19
CN112516998B true CN112516998B (en) 2023-04-07

Family

ID=75000954

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011495148.9A Active CN112516998B (en) 2020-12-17 2020-12-17 Volatile organic pollution gas purification catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112516998B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115849452B (en) * 2022-11-22 2024-06-25 中钢天源股份有限公司 Preparation method of high-specific-surface and high-dispersity manganous oxide and product thereof
CN117920250A (en) * 2024-01-11 2024-04-26 阜阳师范大学 Defect-rich persulfate catalyst and preparation method and application thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101346765B1 (en) * 2010-12-31 2013-12-31 충남대학교산학협력단 Preparation of Lithium-manganese oxide type epoxy sphere composite by using spray drying and template carbonization
CN102060333B (en) * 2011-02-18 2012-05-30 中山火炬职业技术学院 Method for preparing manganese oxide nano-material
WO2012167280A1 (en) * 2011-06-03 2012-12-06 The Regents Of The University Of California Manganese oxide and activated carbon fibers for removing particle, voc or ozone from a gas
CN103399066A (en) * 2013-08-15 2013-11-20 无锡百灵传感技术有限公司 Preparation method of electrochemical sensor based on hausmannite-type manganese oxide nano structure for sodium ion detection
CN109012656B (en) * 2018-08-07 2021-03-30 广东工业大学 Ordered mesoporous gamma-MnO2Catalyst, preparation method and application thereof
CN109745996A (en) * 2019-01-16 2019-05-14 山东大学 Preparation method of high-specific-surface-area nanoscale manganese ferrite catalyst
CN111799462A (en) * 2020-07-10 2020-10-20 山东交通学院 Preparation method of metal manganese oxide/graphene composite electrode material

Also Published As

Publication number Publication date
CN112516998A (en) 2021-03-19

Similar Documents

Publication Publication Date Title
CN112516998B (en) Volatile organic pollution gas purification catalyst and preparation method and application thereof
CN105642299A (en) Nickel-doped lanthanum ferrite/clay nano-structure composite and preparation method and application thereof
CN112076738B (en) Boron-doped defective zinc oxide and preparation method and application thereof
CN111715302B (en) Poisoning-resistant metal oxide denitration catalyst and preparation method thereof
CN111686774B (en) High-stability monatomic platinum-based catalytic material, preparation method and application in purification of oxygen-containing volatile hydrocarbon
CN113275034A (en) Hierarchical pore molecular sieve catalyst for eliminating VOCs and preparation method thereof
CN115770567A (en) Manganese oxide catalyst and preparation method and application thereof
CN111545188A (en) Amorphous aluminosilicate-based denitration catalyst and preparation method thereof
CN101380575B (en) High stability nano gold catalyst for CO normal temperature oxidation and preparation method thereof
CN110404542A (en) A kind of core-shell structure copolymer ball CoFe2O4Catalyst and the preparation method and application thereof
CN102335601B (en) SCR (Silicon Controlled Rectifier) denitration catalyst with mesostructured cellular foam structure and preparation method thereof
CN110721685B (en) Composite photocatalytic material and preparation method and application thereof
CN110548502B (en) Vanadium oxide modified manganese-based catalyst for low-temperature SCR denitration and preparation method and application thereof
CN106799225A (en) A kind of potassium support type soot combustion catalyst and its preparation method and application
CN114849698B (en) Mesoporous Na-alpha-MnO 2 Catalyst, preparation method and application thereof
CN114602477B (en) For CO 2 Double-shell hollow copper-zinc-based catalyst for preparing methanol at low temperature and preparation method thereof
CN111266104B (en) Composite manganese oxide and preparation method and application thereof
CN108097302B (en) Hollow high-dispersion Fe @ Beta molecular sieve catalyst and preparation method and application thereof
CN114452998B (en) Preparation method and application of multiwall carbon nanotube and graphitized carbon nitride composite material
CN115318286A (en) Platinum catalyst for propane catalytic combustion and preparation method and application thereof
CN114029064A (en) Preparation method and application of super-hydrophobic porous copper-indium catalyst
CN109603904B (en) Preparation and application of high-efficiency adipic acid flue gas purification catalyst
CN110961117A (en) Cu-Mn-O-SiO2-Al2O3Preparation method and application of catalyst
CN114054017B (en) Bi plasma modified bismuth strontium tantalate photocatalyst and preparation method thereof
US20240228309A1 (en) Porous ammonia synthesis catalyst, its preparation method and use

Legal Events

Date Code Title Description
PB01 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