CN106430714B - Method for advanced treatment of pesticide wastewater - Google Patents

Method for advanced treatment of pesticide wastewater Download PDF

Info

Publication number
CN106430714B
CN106430714B CN201610947043.XA CN201610947043A CN106430714B CN 106430714 B CN106430714 B CN 106430714B CN 201610947043 A CN201610947043 A CN 201610947043A CN 106430714 B CN106430714 B CN 106430714B
Authority
CN
China
Prior art keywords
wastewater
adsorption
stirring
ammonia nitrogen
cod
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
Application number
CN201610947043.XA
Other languages
Chinese (zh)
Other versions
CN106430714A (en
Inventor
何丹农
严良
童琴
代卫国
高小迪
金彩虹
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.)
Shanghai Na Xu Industrial Co Ltd
Original Assignee
Shanghai Na Xu Industrial Co Ltd
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 Shanghai Na Xu Industrial Co Ltd filed Critical Shanghai Na Xu Industrial Co Ltd
Priority to CN201610947043.XA priority Critical patent/CN106430714B/en
Publication of CN106430714A publication Critical patent/CN106430714A/en
Application granted granted Critical
Publication of CN106430714B publication Critical patent/CN106430714B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F2101/306—Pesticides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Water Treatment By Sorption (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention discloses a method for deeply treating pesticide wastewater, which comprises the steps of firstly adopting Fenton oxidation for pretreatment, and then combining adsorption flocculation to efficiently remove CODCrAnd the effect of ammonia nitrogen. According to the invention, the Fenton reagent is improved, so that the oxidative degradation capability is improved; adsorption flocculationIn the agent, alum reacts with sodium silicate to generate flocculated sediment of aluminum hydroxide and silicic acid (silicon dioxide), and is combined with nonionic polyacrylamide and active carbon, so that the adsorption and flocculation effects are improved; the sodium silicate replaces weak alkalis such as ammonia water, carbonate and the like, thereby avoiding causing ammonia nitrogen content and COD of the wastewaterCrAnd (4) rising. The method is applied to the advanced treatment of pesticide wastewater, has strong effects of oxidative degradation and adsorption flocculation, and can be used for treating COD of wastewaterCrAnd the removal rate of ammonia nitrogen content is high.

Description

Method for advanced treatment of pesticide wastewater
Technical Field
The invention relates to a method for deeply treating pesticide wastewater, in particular to a method for deeply treating pesticide wastewater by an efficient oxidation-adsorption flocculation method.
Background
The pesticide wastewater is wastewater discharged by a pesticide factory in the pesticide production process, and the quality and the quantity of the wastewater are unstable; higher concentration of pollutants, CODCrHigher; the toxicity is high, and the wastewater contains toxic substances such as phenol, arsenic, mercury and the like and a plurality of substances which are difficult to biodegrade besides pesticides and intermediates; has the characteristics of stink, irritation to the respiratory tract and the mucous membrane of people and the like, thereby becoming a difficulty in scientific research. According to statistics, the annual discharged wastewater amount of national pesticide production enterprises is nearly 2.0 hundred million tons, wherein the treated wastewater accounts for 7 percent of the total amount, the treated wastewater reaches the standard and only accounts for 1 percent of the treated wastewater, and along with the annual increase of the pesticide yield in China, the environmental pollution and the deterioration of an ecological system caused by pesticide wastewater are increasingly severe. Therefore, the research on new methods and new processes for treating pesticide wastewater becomes a research hotspot which is beneficial to the livelihood of the people.
At present, the methods for treating pesticide wastewater at home and abroad mainly comprise physical methods (adsorption method and membrane separation method), chemical methods, biochemical methods (aerobic biological treatment and anaerobic biological treatment) and new methods (photocatalytic oxidation method, magnetic separation method, ultrasonic technology and the like). However, the most common adsorbent used in the adsorption method is activated carbon, which has high treatment cost and difficult regeneration; if the membrane separation technology is adopted, the one-time investment is large, the technical difficulty is large, the membrane system is difficult to clean, the water quantity required by backwashing is large, and the operation and maintenance cost is high; the biological method has low operation cost, but has large fluctuation of treatment effect, long period, high concentration of organic matters in the pesticide wastewater and great toxicity to microorganisms; if the photocatalytic oxidation method is adopted, the degradation speed is high, secondary pollution is not generated, the reaction condition is mild, but the photocatalyst generally needs ultraviolet light as energy, the energy consumption is high, the turbidity of the pesticide wastewater is high, the light transmittance is poor, the light absorption rate is influenced, the recovery rate of the photocatalyst is low, and the magnetic separation method and the ultrasonic technology are still in the laboratory research stage in China, so that the application of the magnetic separation method and the ultrasonic technology in the pesticide wastewater treatment is limited.
The Fenton oxidation technology has the advantages of easy damage of chemical structures of refractory organic matters in the wastewater, high treatment efficiency, no secondary pollution, simple operation and the like, thereby having certain applicability to the treatment of high-concentration industrial wastewater. The traditional chemical coagulation process comprises coagulation and flocculation, the treatment effect on soluble organic pollutants is not ideal, and the adsorption flocculant can be quickly bridged in sewage to form floccules, and the floccules are quickly precipitated and separated to be removed after pollutants are adsorbed on the surface of the floccules.
Based on this, the Fenton technology pretreatment and the adsorption flocculation process are combined, so that the limitation of a single technology is overcome, the Fenton oxidation, adsorption, flocculation precipitation and other effects are comprehensively exerted to treat the pesticide wastewater, and the COD of the pesticide wastewater is efficiently reducedCrAnd ammonia nitrogen.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to: provides a method for the advanced treatment of pesticide wastewater, which adopts a process route combining Fenton oxidation pretreatment and adsorption flocculation to carry out the advanced treatment of the pesticide wastewater.
Yet another object of the present invention is: provides an adsorption flocculant for the method for deeply treating the pesticide wastewater.
The purpose of the invention is realized by the following scheme:
a process for deeply treating the sewage generated by agricultural chemical includes such steps as pretreating by Fenton oxidization, and adsorbing by adsorptionThe coagulant can efficiently remove CODCrAnd the effect of ammonia nitrogen.
The Fenton reagent consists of potassium ferrate or a mixture of potassium ferrate and hydrated ferrous sulfate and hydrogen peroxide.
The Fenton oxidation pretreatment process comprises the following steps: according to 500mL of wastewater, firstly, 10% dilute sulfuric acid is used for adjusting the pH value of the wastewater to 2-3, and then 100-125 mg/L potassium ferrate or a mixture of the potassium ferrate and ferrous sulfate heptahydrate (or ferrous sulfate dodecahydrate) is added; stirring for 2min, standing for 20min, adding 800-1000 mg/L hydrogen peroxide in batches for oxidative degradation for 1h, and adding alkali liquor to adjust the pH value of 7-8; and then, adding 19.5-26 g of an adsorption flocculant, stirring for 2min, standing for 20min, and finishing the advanced treatment of the pesticide wastewater with the wastewater amount of 500 mL.
On the basis of the scheme, the adsorption flocculant is formed by compounding a flocculant and an adsorbent, wherein the flocculant is formed by combining alum, nonionic polyacrylamide and sodium silicate, and the adsorbent is powdered activated carbon.
The specific preparation method of the adsorption flocculant comprises the following steps: dissolving 50g of alum in 195g of water, adding 0.1g of nonionic polyacrylamide and 100g of powdered activated carbon into the alum solution, wherein the particle size of the powdered activated carbon is 170 meshes or more, stirring at 40-60 ℃ at 200 r/min for 30 min, adding 45g of sodium silicate, stirring for 60min, and standing for 2-3 h to obtain the adsorption flocculant.
The alkali liquor is 10% calcium oxide suspension.
The method of the invention can ensure that the pesticide wastewater CODCrAnd the removal rate of ammonia nitrogen reaches more than 90.0 percent and 80.0 percent respectively.
The oxidation-adsorption flocculation technology provided by the invention is mainly applied to the advanced treatment of pesticide wastewater and is also applicable to the treatment of other industrial wastewater.
Compared with the prior art, the invention has the following advantages:
fenton oxidation and adsorption flocculation are combined, and the effects of oxidative degradation, adsorption and flocculation precipitation are comprehensively exerted; adding potassium ferrate or potassium ferrate/ferrous sulfate dodecahydrate mixture to replace traditional Fe2+Can exert the potassium ferrate oxygenFlocculation, precipitation, Fe produced by redox processes2+Can also be used for H2O2The catalyst plays a role in generating hydroxyl free radicals with strong oxidizing property; the 10% calcium oxide suspension is used as alkali liquor to regulate pH value of waste water, and can also have coagulation-promoting effect on colloidal particles in waste water, and can be used as particle nucleus weighting agent to accelerate separation of insoluble substances. The aluminum hydroxide and the silicic acid (silicon dioxide) generated by the reaction of the alum and the sodium silicate are precipitated in a flocculation manner and combined with the nonionic polyacrylamide and the activated carbon, so that the adsorption and flocculation effects are improved, the sodium silicate is used for replacing weak bases such as traditional ammonia water and sodium carbonate, the ammonia nitrogen content of the wastewater is not increased, and the COD (chemical oxygen demand) is not increased due to the introduction of carbonateCrAnd (4) rising. The oxidation-adsorption flocculation method of the invention can be used for not only the advanced treatment of pesticide wastewater, but also the treatment of other industrial wastewater, and has certain reference significance in the water treatment industry.
Detailed Description
The following examples illustrate the invention in detail: the present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
Example 1:
dissolving 50g of alum in 195g of water, adding 0.1g of nonionic polyacrylamide and 100g of powdered activated carbon (170 meshes) into the alum solution, stirring at 50 ℃ for 30 min at 200 r/min, adding 45g of sodium silicate, stirring for 60min, and standing for 2 h to obtain the adsorption flocculant.
Firstly, 10% dilute sulfuric acid is used for adjusting the pH value of the wastewater to 3, then 100 mg/L potassium ferrate is added, the stirring is carried out for 2min, the standing is carried out for 20min, 800 mg/L hydrogen peroxide is added in batches for carrying out oxidative degradation for 1h, 10% calcium oxide suspension is added for adjusting the pH value to 8, 19.5 g of adsorption flocculant is added, the stirring is carried out for 2min, and the standing is carried out for 20 min. CODCrThe removal rate is 92.1 percent, and the removal rate of ammonia nitrogen is 80.4 percent.
Example 2:
dissolving 50g of alum in 195g of water, adding 0.1g of nonionic polyacrylamide and 100g of powdered activated carbon (170 meshes) into the alum solution, stirring at 50 ℃ for 30 min at 200 r/min, adding 45g of sodium silicate, stirring for 60min, and standing for 3h to obtain the adsorption flocculant.
Firstly, 10% dilute sulfuric acid is used for adjusting the pH value of the wastewater to 2, then 80 mg/L potassium ferrate is added firstly, the stirring is carried out for 2min, the standing is carried out for 20min, then 20 mg/L ferrous sulfate heptahydrate and 800 mg/L hydrogen peroxide are added in batches for carrying out oxidative degradation for 1h, 10% calcium oxide suspension is added for adjusting the pH value to 7, then 26g of adsorption flocculant is added, the stirring is carried out for 2min, and the standing is carried out for 20 min. CODCrThe removal rate is 94.6%, and the removal rate of ammonia nitrogen is 82.5%.
Example 3:
dissolving 50g of alum in 195g of water, adding 0.1g of nonionic polyacrylamide and 100g of powdered activated carbon (200 meshes) into the alum solution, stirring at 50 ℃ for 30 min at 200 r/min, adding 45g of sodium silicate, stirring for 60min, and standing for 2 h to obtain the adsorption flocculant.
Firstly, 10% dilute sulfuric acid is used for adjusting the pH value of the wastewater to 3, then 100 mg/L potassium ferrate is added, the stirring is carried out for 2min, the standing is carried out for 20min, 800 mg/L hydrogen peroxide is added in batches for carrying out oxidative degradation for 1h, 10% calcium oxide suspension is added for adjusting the pH value to 8, 19.5 g of adsorption flocculant is added, the stirring is carried out for 2min, and the standing is carried out for 20 min. CODCrThe removal rate is 93.4%, and the removal rate of ammonia nitrogen is 81.7%.
Example 4:
dissolving 50g of alum in 195g of water, adding 0.1g of nonionic polyacrylamide and 100g of powdered activated carbon (200 meshes) into the alum solution, stirring at 50 ℃ for 30 min at 200 r/min, adding 45g of sodium silicate, stirring for 60min, and standing for 3h to obtain the adsorption flocculant.
Firstly, 10% dilute sulfuric acid is used for adjusting the pH value of the wastewater to 2, then 80 mg/L potassium ferrate is added firstly, the stirring is carried out for 2min, the standing is carried out for 20min, then 20 mg/L ferrous sulfate heptahydrate and 800 mg/L hydrogen peroxide are added in batches for carrying out oxidative degradation for 1h, 10% calcium oxide suspension is added for adjusting the pH value to 7, then 26g of adsorption flocculant is added, the stirring is carried out for 2min, and the standing is carried out for 20 min. CODCrThe removal rate is 96.3 percent, and the removal rate of ammonia nitrogen is 84.1 percent.

Claims (2)

1. The method for deeply treating the pesticide wastewater is characterized by firstly adopting a Fenton reagent for oxidation pretreatment and then combining an adsorption flocculant to remove COD (chemical oxygen demand)CrAnd ammonia nitrogen, wherein,
the Fenton reagent consists of potassium ferrate or a mixture of potassium ferrate and hydrated ferrous sulfate and hydrogen peroxide;
according to 500mL of wastewater, the Fenton reagent firstly uses 10% dilute sulfuric acid to adjust the pH value of the wastewater to 2-3, and then 100-125 mg/L potassium ferrate or a mixture of 80 mg/L potassium ferrate and 20 mg/L ferrous sulfate heptahydrate is added in batches; stirring for 2min, standing for 20min, adding 800-1000 mg/L hydrogen peroxide in batches for oxidative degradation for 1h, adding alkali liquor to adjust the pH value of 7-8, then adding 19.5-26 g of adsorption flocculant, stirring for 2min, and standing for 20 min;
adsorbing flocculant, dissolving 50g of alum in 195g of water, adding 0.1g of nonionic polyacrylamide and 100g of powdered activated carbon with the particle size of 170 meshes or more into the alum solution, stirring at the temperature of 50 ℃ at 200 r/min for 30 min, adding 45g of sodium silicate, stirring for 60min, and standing for 2 h or 3h to obtain the adsorbing flocculant;
make CODCrThe removal rate is more than 92.1 percent, and the ammonia nitrogen removal rate is more than 80.4 percent.
2. The method for the advanced treatment of pesticide wastewater as claimed in claim 1, wherein the alkali liquor is a 10% calcium oxide suspension.
CN201610947043.XA 2016-10-26 2016-10-26 Method for advanced treatment of pesticide wastewater Expired - Fee Related CN106430714B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610947043.XA CN106430714B (en) 2016-10-26 2016-10-26 Method for advanced treatment of pesticide wastewater

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610947043.XA CN106430714B (en) 2016-10-26 2016-10-26 Method for advanced treatment of pesticide wastewater

Publications (2)

Publication Number Publication Date
CN106430714A CN106430714A (en) 2017-02-22
CN106430714B true CN106430714B (en) 2020-02-14

Family

ID=58178508

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610947043.XA Expired - Fee Related CN106430714B (en) 2016-10-26 2016-10-26 Method for advanced treatment of pesticide wastewater

Country Status (1)

Country Link
CN (1) CN106430714B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107892408A (en) * 2017-10-10 2018-04-10 华北理工大学 A kind of farmland agricultural chemicals waste water purification method
CN108314208B (en) * 2018-02-01 2021-10-01 太原理工大学 Method for oxidizing and flocculating phenanthrene and coal particles in coking wastewater by using Fe (VI)/Fenton system
CN112939167A (en) * 2021-01-29 2021-06-11 安道麦安邦(江苏)有限公司 Composite coagulant for treating organic phosphorus in pesticide wastewater, preparation method and application

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102399032A (en) * 2010-09-07 2012-04-04 中国石油化工股份有限公司 Method for treating organic amine industrial waste water by Fenton-like oxidation-flocculation

Also Published As

Publication number Publication date
CN106430714A (en) 2017-02-22

Similar Documents

Publication Publication Date Title
CN100494098C (en) Fenton and air-float integral water treating method
CN103787537B (en) A kind for the treatment of process of sewage and application thereof
CN109095732B (en) Process for preparing high-purity magnesium hydroxide based on magnesium-method desulfurization wastewater
CN106430714B (en) Method for advanced treatment of pesticide wastewater
CN109081518B (en) Method for treating hexavalent chromium pollution in water
CN106977013B (en) Purification treatment method of high-chlorine thallium-containing wastewater and application thereof
CN112723520A (en) Recovery and reuse method of Fenton reaction iron mud and Fenton reagent prepared by adopting method
CN109437386B (en) Method for removing metal thallium in wastewater
CN110862182A (en) Landfill leachate treatment device and method
CN105692967B (en) A kind of processing method of PVA process units waste water
CN104860455B (en) A kind of dithiocyano-methane method of wastewater treatment
CN105254067B (en) The resource utilization method of advanced treatment of wastewater Fenton process sludge
CN111439767A (en) Efficient preparation method for preparing aluminum sulfate by using waste
CN110156237A (en) A kind of waste water water conservancy recovery method
CN106630312B (en) Treatment system, treatment method and application of coking phenol-cyanogen wastewater
CN105110515A (en) Treatment method of DSD (4, 4'-Diaminostilbene-2, 2'-disulfonic) acid wastewater
CN108928984B (en) Method for realizing zero emission of reverse osmosis strong brine in iron and steel enterprises
CN112960796A (en) Method for removing sulfadimidine in wastewater
CN107344748B (en) Method for treating reverse osmosis concentrated solution by using secondary iron mineral activated peroxymonosulfate
CN106186552A (en) The advanced treatment process of petrochemical wastewater
CN106629971B (en) Iron-based nano sewage treatment agent and application method thereof
CN114105396A (en) Process method for efficiently treating Lyocell short fiber wastewater
CN210945260U (en) Processing system of rubber auxiliary M waste water
CN113117680B (en) Nano ferrous metatitanate-silica gel particle Fenton catalyst, and preparation method and application method thereof
CN108117235B (en) Pesticide wastewater treatment system and process

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into 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: 20200214

Termination date: 20201026