CN108295839B - Preparation method and application of catalyst composition for degrading low-concentration formaldehyde in wastewater - Google Patents
Preparation method and application of catalyst composition for degrading low-concentration formaldehyde in wastewater Download PDFInfo
- Publication number
- CN108295839B CN108295839B CN201711418276.1A CN201711418276A CN108295839B CN 108295839 B CN108295839 B CN 108295839B CN 201711418276 A CN201711418276 A CN 201711418276A CN 108295839 B CN108295839 B CN 108295839B
- Authority
- CN
- China
- Prior art keywords
- formaldehyde
- wastewater
- catalyst composition
- solution
- composite oxide
- 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.)
- Expired - Fee Related
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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method and application of a catalyst composition for degrading low-concentration formaldehyde in wastewater. The composite oxide in the catalyst composition is a cerium tin manganese composite oxide catalyst composite oxide. The method comprises the following steps: 1. dissolving raw materials and alkalifying the solution; 2. heating the potassium persulfate solution; 3. drying; 4. and (4) calcining. The catalyst composition has high activity, can quickly and efficiently catalyze, oxidize and degrade formaldehyde in wastewater in a short time, can be used for treating wastewater at normal temperature and normal pressure without oxidant and illumination, has the characteristics of simple process flow, no secondary pollution, low operation cost and the like, can be repeatedly used for many times, and has high practical application value.
Description
The technical field is as follows:
the invention relates to the field of inorganic material preparation, in particular to a preparation method and application of a catalyst composition for degrading low-concentration formaldehyde in wastewater.
Background art:
formaldehyde is readily soluble in water and has a strong pungent odor. It is an important chemical raw material, and can be extensively used in the fields of disinfection, sterilization, anticorrosion, pharmacy, pesticide, dye, plastics and building industry, etc. Formaldehyde, however, is highly toxic and has been identified by the world health organization as a carcinogenic and teratogenic substance. At present, as a method for removing formaldehyde in wastewater, there are an adsorption method, an ozone oxidation method, a photocatalytic method, a thermal wet oxidation method, a biological method, a stripping method, and the like. The adsorption method has poor selectivity and difficult regeneration. Ozone used in the ozone oxidation method is extremely harmful to human health. Photocatalytic treatment requires the use of a specific excitation light source. The titanium dioxide photocatalysts which are most widely used at present can only utilize ultraviolet light. The heat-wet oxidation process is high in energy consumption. The biological method has low treatment cost, but has slow reaction speed and large floor area of treatment facilities. The blow-off method has poor effect.
Catalytic oxidation of formaldehyde at room temperature is an effective way to remove formaldehyde. In recent years, there has been considerable interest, but the catalysts of this process all comprise at least one noble metal. Pt/SnO invented by US patent US55850832The catalyst can completely degrade formaldehyde into carbon dioxide and water at room temperature, but the catalyst contains 12% of noble metal Pt by mass fraction. Chinese patent CN103071489A discloses a preparation method of a supported activated carbon catalytic material for removing formaldehyde at room temperature, wherein the catalytic material contains 0.1-2% of precious metal active components of one or the combination of gold, palladium, platinum, rhodium and ruthenium. Chinese patent CN102139234A discloses a supported catalyst for removing formaldehyde at room temperature, the active component of the supported catalyst is one or more noble metals of gold, palladium, platinum, rhodium and ruthenium,the content of the noble metal accounts for 0.1-2% of the weight of the catalyst. The precious metal resources are rare and the price is high, which limits the popularization and application of catalytic oxidation for removing formaldehyde in the greenhouse.
The invention content is as follows:
the invention aims to provide a preparation method and application of a catalyst composition for degrading low-concentration formaldehyde in wastewater. In view of the above, the present invention is designed to solve the above technical problems in the prior art, and provide a preparation method and application of a catalyst composition for simply and effectively treating formaldehyde in wastewater.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a catalyst composition for degrading low-concentration formaldehyde in wastewater comprises a composite oxide, wherein the composite oxide in the catalyst composition is a cerium-tin-manganese composite oxide, and the composite oxide serving as a catalyst can catalyze, oxidize and degrade the formaldehyde in the wastewater.
A preparation method of a catalyst composition for degrading low-concentration formaldehyde in wastewater comprises the following steps:
1. raw material dissolution and solution alkalization: taking cerium sulfate, tin tetrachloride and manganese nitrate as raw materials, adding deionized water into a beaker, stirring until the deionized water is dissolved, and then dropwise adding ammonia water with the concentration of 6mol/L until the solution is alkalescent, wherein the pH value is 8-10;
2. heating the potassium persulfate solution: adding 5mL of potassium persulfate solution with the volume percentage concentration of 5% into the alkalescent solution obtained in the step 1, heating to boil, cooling to room temperature, and then carrying out suction filtration;
3. drying: putting the precipitate obtained in the step 2 into an oven to be dried at the temperature of 105-150 ℃;
4. and (3) calcining: and (4) putting the dried precipitate obtained in the step (3) into a muffle furnace, calcining for 3-8 hours at the temperature of 300-900 ℃, and calcining to obtain cerium-tin-manganese composite oxide powder.
The molar ratio of cerium sulfate, tin tetrachloride and manganese nitrate in the method is 21.1:18.9: 1.0.
the application of the catalyst composition for degrading low-concentration formaldehyde in wastewater is characterized in that: adding the obtained cerium-tin-manganese composite oxide into the wastewater according to the proportion of 0.5-4.0 g/L, and stirring for 30-60 minutes at normal temperature and normal pressure.
The method for treating the formaldehyde wastewater by applying the cerium-tin-manganese composite oxide catalyst disclosed by the invention comprises the following steps of: taking the composite oxide as a catalyst, and the degradation reaction conditions are as follows: the concentration of formaldehyde is less than 5%, the dosage of a catalyst for treating formaldehyde wastewater per liter is 0.5-4.0 g, and a wastewater system is at normal temperature and normal pressure. In the test, when the volume of the formaldehyde wastewater is 40mL and the concentration is 1.0%, 0.1g of the catalyst is added under stirring, the catalytic degradation is carried out for 30 minutes, and the degradation rate of the formaldehyde reaches more than 90%. And replacing the residual solution with a new formaldehyde solution and then recycling the catalyst. The result shows that the degradation rate of formaldehyde of the catalyst in the second circulation and the third circulation reaches more than 90.0 percent.
Compared with the prior art, the invention has the positive effects that
1. The catalyst composition used in the invention has simple preparation method, low cost of raw materials and convenient operation;
2. the catalyst composition prepared by the invention has high activity, and can quickly and efficiently degrade pollutants in a short time;
3. the wastewater treatment method can be carried out at normal temperature and normal pressure without oxidant or illumination, has the characteristics of simple process flow, no secondary pollution, low operation cost and the like, and has high practical application value;
4. the catalyst composition prepared by the invention can be repeatedly used for many times.
Detailed Description
The technical solution of the present invention is further clearly and completely described below with reference to the following examples.
Example 1:
1. dissolving the raw materials and alkalifying the solution, weighing 4.04g (1.0 × 10)-2mol) cerium sulfate, 3.15g (8.98 × 10)- 3mol) tin tetrachloride pentahydrate and 0.17g (4.75 × 10)-4mol) manganese nitrate (50% solution), in a beaker by adding deionizationStirring the water until the water is completely dissolved, and then dropwise adding ammonia water with the concentration of 6mol/L until the pH value is 8-10;
2. heating the potassium persulfate solution: adding 5mL of potassium persulfate with the volume percentage concentration of 5% into the alkalescent solution obtained in the step 1, heating to boil, cooling to room temperature, and then carrying out suction filtration;
3. drying: putting the precipitate obtained in the step 2 into an oven to be dried at the temperature of 105-150 ℃;
4. and (3) calcining: and (4) putting the dried precipitate obtained in the step (3) into a muffle furnace, and calcining for 8 hours at 300 ℃ to obtain cerium-tin-manganese composite oxide powder.
0.1g of the cerium-tin-manganese composite oxide catalyst prepared by the method is added into formaldehyde wastewater with the volume of 40mL and the concentration of 1.0 percent, and formaldehyde is catalytically degraded for 30 minutes under the stirring action at normal temperature and pressure. The mixture was then centrifuged in a centrifuge for 10 minutes, and the supernatant was taken to measure the residual concentration of formaldehyde. As a result, as shown in Table 1, the formaldehyde degradation rate was 90.9% when the degradation time was 30 minutes.
TABLE 1 degradation time and degradation rate of Formaldehyde in wastewater
| Catalyst degradation time/min | 15 | 30 | 45 | 60 |
| Percent formaldehyde degradation/%) | 86.6 | 90.9 | 92.1 | 93.5 |
Example 2
1. Dissolving the raw materials and alkalifying the solution, weighing 4.04g (1.0 × 10)-2mol) cerium sulfate, 3.15g (8.98 × 10)- 3mol) tin tetrachloride pentahydrate and 0.17g (4.75 × 10)-4mol) manganese nitrate (50% solution), adding deionized water into a beaker, stirring until the solution is completely dissolved, and then dropwise adding ammonia water with the concentration of 6mol/L until the pH value is 8-10;
2. heating the potassium persulfate solution: adding 5mL of potassium persulfate with the volume percentage concentration of 5% into the alkalescent solution obtained in the step 1, heating to boil, cooling to room temperature, and then carrying out suction filtration;
3. drying: putting the precipitate obtained in the step 2 into an oven to be dried at the temperature of 105-150 ℃;
4. and (3) calcining: and (4) putting the dried precipitate obtained in the step (3) into a muffle furnace, and calcining for 5 hours at 750 ℃ to obtain cerium-tin-manganese composite oxide powder.
0.1g of the cerium-tin-manganese composite oxide catalyst prepared by the method is added into formaldehyde wastewater with the volume of 40mL and the concentration of 1.0 percent, and formaldehyde is catalytically degraded for 30 minutes under the stirring action at normal temperature and pressure. The mixture was then centrifuged in a centrifuge for 10 minutes, and the supernatant was taken to measure the residual concentration of formaldehyde. When the degradation time was 30 minutes, the formaldehyde degradation rate was 93.7%.
Example 3
1. Dissolving the raw materials and alkalifying the solution, weighing 4.04g (1.0 × 10)-2mol) cerium sulfate, 3.15g (8.98 × 10)- 3mol) tin tetrachloride pentahydrate and 0.17g (4.75 × 10)-4mol) manganese nitrate (50% solution), adding deionized water into a beaker, stirring until the solution is completely dissolved, and then dropwise adding ammonia water with the concentration of 6mol/L until the pH value is 8-10;
2. heating the potassium persulfate solution: adding 5mL of potassium persulfate with the volume percentage concentration of 5% into the alkalescent solution obtained in the step 1, heating to boil, cooling to room temperature, and then carrying out suction filtration;
3. drying: putting the precipitate obtained in the step 2 into an oven to be dried at the temperature of 105-150 ℃;
4. and (3) calcining: and (4) putting the dried precipitate obtained in the step (3) into a muffle furnace, and calcining at 900 ℃ to obtain cerium-tin-manganese composite oxide powder.
0.1g of the cerium-tin-manganese-iron composite oxide catalyst prepared by the method is added into formaldehyde wastewater with the volume of 40mL and the concentration of 1.0 percent, and formaldehyde is catalytically degraded for 30 minutes under the stirring action at normal temperature and pressure. The mixture was then centrifuged in a centrifuge for 10 minutes, and the supernatant was taken to measure the residual concentration of formaldehyde. When the degradation time is 30 minutes, the formaldehyde degradation rate is 92.8%.
Example 4
In order to examine the recycling condition of the catalyst composition, the cerium-tin-manganese composite oxide obtained by the preparation method of the catalyst described in example 2 was subjected to three consecutive catalytic oxidative degradation tests of formaldehyde, each degradation time being 30 minutes.
0.10g of cerium-tin-manganese oxide catalyst is added into a beaker containing 40mL of 1.0% formaldehyde solution, and formaldehyde is catalytically degraded under the action of stirring at normal temperature and pressure for 30 minutes under the action of magnetic stirring. The mixture was then centrifuged in a centrifuge for 10 minutes, and the supernatant was taken to measure the residual concentration of formaldehyde. The centrifuged supernatant was aspirated with a dropper to leave only the catalyst solid, 40mL of a new 1.0% formaldehyde solution was added, and the above formaldehyde degradation process was repeated, so that the second cycle and the third cycle of formaldehyde degradation tests were performed, and the results are shown in Table 2.
TABLE 2 catalyst Cyclic degradation of Formaldehyde
| Number of times of catalyst use | 1 | 2 | 3 |
| Percent formaldehyde degradation/%) | 93.7 | 92.6 | 91.9 |
As can be seen from Table 2, the degradation rate of the catalyst for degrading formaldehyde in three cycles is over 90.0%, which shows that the cerium-tin-manganese composite oxide catalyst can be recycled.
All of the features disclosed in this specification, or all of the methods of manufacture and uses disclosed, may be combined in any combination, except combinations and/or steps, or uses thereof, which are mutually exclusive. Any feature disclosed in this specification (including any accompanying claims and abstract) may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
The above description is only a non-limiting embodiment of the invention, and many embodiments can be derived, and those skilled in the art can make several modifications and improvements without departing from the inventive concept and without making creative efforts, which all belong to the protection scope of the present invention.
Claims (2)
1. A preparation method of a catalyst composition for degrading low-concentration formaldehyde in wastewater is characterized by comprising the following steps: the method comprises the following steps:
(1) raw material dissolution and solution alkalization: taking cerium sulfate, tin tetrachloride and manganese nitrate as raw materials, adding deionized water into a beaker, stirring until the mixture is dissolved, and then dropwise adding ammonia water with the concentration of 6mol/L until the solution is weakly alkaline, wherein the molar ratio of the cerium sulfate to the tin tetrachloride to the manganese nitrate is 21.1:18.9:1.0, and the pH value is 8-10;
(2) heating the potassium persulfate solution: adding 5mL of potassium persulfate solution with the volume percentage concentration of 5% into the weak alkaline solution obtained in the step (1), heating to boil, cooling to room temperature, and performing suction filtration;
(3) drying: putting the precipitate obtained in the step (2) into an oven to be dried at the temperature of 105-150 ℃;
(4) and (3) calcining: and (4) putting the dried precipitate obtained in the step (3) into a muffle furnace, calcining for 3-8 hours at the temperature of 300-900 ℃, and calcining to obtain cerium-tin-manganese composite oxide powder.
2. The application of the catalyst composition for degrading low-concentration formaldehyde in wastewater prepared by the method according to claim 1 is characterized in that: adding the obtained cerium-tin-manganese composite oxide into formaldehyde wastewater according to the proportion of 0.5-4.0 g/L, and stirring at normal temperature and normal pressure for 30-60 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711418276.1A CN108295839B (en) | 2017-12-25 | 2017-12-25 | Preparation method and application of catalyst composition for degrading low-concentration formaldehyde in wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711418276.1A CN108295839B (en) | 2017-12-25 | 2017-12-25 | Preparation method and application of catalyst composition for degrading low-concentration formaldehyde in wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108295839A CN108295839A (en) | 2018-07-20 |
| CN108295839B true CN108295839B (en) | 2020-09-11 |
Family
ID=62870421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711418276.1A Expired - Fee Related CN108295839B (en) | 2017-12-25 | 2017-12-25 | Preparation method and application of catalyst composition for degrading low-concentration formaldehyde in wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108295839B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113181904A (en) * | 2021-05-07 | 2021-07-30 | 南京信息工程大学 | Catalyst for degrading medical wastewater at room temperature |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103071489A (en) * | 2011-10-25 | 2013-05-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Supported active carbon catalytic material capable of eliminating formaldehyde at room temperature and preparation method thereof |
| CN103599793A (en) * | 2013-11-28 | 2014-02-26 | 天津市环境保护科学研究院 | Supported copper-manganese composite oxide catalyst capable of removing formaldehyde at room temperature and preparation method |
| CN106238065A (en) * | 2016-07-08 | 2016-12-21 | 宁波钛安新材料科技有限公司 | A kind of composite catalyst being catalyzed Formaldehyde decomposition and preparation method thereof |
| CN106622260A (en) * | 2016-12-09 | 2017-05-10 | 湖北工业大学 | Preparation method and application of catalyst for treating low-concentration formaldehyde wastewater |
| CN106824172A (en) * | 2016-12-09 | 2017-06-13 | 湖北工业大学 | The carbon monoxide-olefin polymeric preparation method and application of low concentration formaldehyde in treatment waste water |
-
2017
- 2017-12-25 CN CN201711418276.1A patent/CN108295839B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103071489A (en) * | 2011-10-25 | 2013-05-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Supported active carbon catalytic material capable of eliminating formaldehyde at room temperature and preparation method thereof |
| CN103599793A (en) * | 2013-11-28 | 2014-02-26 | 天津市环境保护科学研究院 | Supported copper-manganese composite oxide catalyst capable of removing formaldehyde at room temperature and preparation method |
| CN106238065A (en) * | 2016-07-08 | 2016-12-21 | 宁波钛安新材料科技有限公司 | A kind of composite catalyst being catalyzed Formaldehyde decomposition and preparation method thereof |
| CN106622260A (en) * | 2016-12-09 | 2017-05-10 | 湖北工业大学 | Preparation method and application of catalyst for treating low-concentration formaldehyde wastewater |
| CN106824172A (en) * | 2016-12-09 | 2017-06-13 | 湖北工业大学 | The carbon monoxide-olefin polymeric preparation method and application of low concentration formaldehyde in treatment waste water |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108295839A (en) | 2018-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106622227B (en) | A kind of preparation method of the monatomic catalyst of indoor air purification | |
| Zamri et al. | Performance studies of electrobiosynthesis of titanium dioxide nanoparticles (TiO2) for phenol degradation | |
| CN102266723B (en) | Regenerating method and regenerating device for selective catalytic reduction de-nitration catalyst | |
| WO2015149499A1 (en) | Low-temperature and highly efficient denitration catalyst and preparation method therefor | |
| CN106824172A (en) | The carbon monoxide-olefin polymeric preparation method and application of low concentration formaldehyde in treatment waste water | |
| CN113144894B (en) | Functional material for visually degrading formaldehyde and VOCs at normal temperature and pressure and preparation method thereof | |
| CN102583634A (en) | Nanometer silver-doped titanium dioxide/chitosan composite microspheres for photolyzing phenol in source water | |
| CN106622260B (en) | A kind of preparation method and application handling low concentration formaldehyde waste water catalyst | |
| CN103028423A (en) | Inactivation and regeneration method of formaldehyde room-temperature oxidation catalyst | |
| CN109011868A (en) | A kind of catalyst system and its application and purification method and purification system | |
| CN108295839B (en) | Preparation method and application of catalyst composition for degrading low-concentration formaldehyde in wastewater | |
| CN108311147A (en) | Preparation method for the perovskite supported noble metal catalyst for purifying benzene | |
| CN108295863B (en) | Preparation method and application of catalyst composition for treating formaldehyde | |
| CN207056335U (en) | A kind of box photo catalysis reactor | |
| CN108355670B (en) | Preparation method and application of catalyst composition for degrading low-concentration formaldehyde | |
| CN107983348A (en) | A kind of efficient ozone decomposition catalyst | |
| CN108246308B (en) | Preparation method and application of catalyst composition for treating low-concentration formaldehyde | |
| CN109433272A (en) | A kind of preparation method of the catalysis material of room temperature removal ozone | |
| CN108654602A (en) | The high-specific surface area platinum of eliminating formaldehyde at room temperature modifies the preparation method of porous carbon-based titanium dioxide catalyst | |
| CN106542584A (en) | A kind of preparation method of rich defect cobalt oxide photocatalyst | |
| CN106076086A (en) | A kind of method of normal-temperature efficient catalytic degradation vehicle spray painting industry VOCs waste gas | |
| CN111054360A (en) | Catalyst for catalytic combustion treatment of PTA tail gas | |
| CN108144628A (en) | A kind of preparation method and application for the carbon monoxide-olefin polymeric for handling formaldehyde in waste water | |
| CN100446853C (en) | Nanometer quaternary photocatalyst for eliminating air pollution in small spaces and the preparing method | |
| Shelimov et al. | Photocatalytic purification of indoor air from nitrogen oxide contaminants on modified TiO2-based catalysts |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200911 Termination date: 20211225 |