CN1095514C - Process for degradating chlorinated lignin and its derivatives - Google Patents
Process for degradating chlorinated lignin and its derivatives Download PDFInfo
- Publication number
- CN1095514C CN1095514C CN00130810A CN00130810A CN1095514C CN 1095514 C CN1095514 C CN 1095514C CN 00130810 A CN00130810 A CN 00130810A CN 00130810 A CN00130810 A CN 00130810A CN 1095514 C CN1095514 C CN 1095514C
- Authority
- CN
- China
- Prior art keywords
- anode
- lignin
- derivatives
- cathode
- chlorinated
- 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
- 229920005610 lignin Polymers 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 18
- 239000002351 wastewater Substances 0.000 claims abstract description 18
- 238000006731 degradation reaction Methods 0.000 claims abstract description 9
- 230000015556 catabolic process Effects 0.000 claims abstract description 8
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010525 oxidative degradation reaction Methods 0.000 claims abstract 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000460 chlorine Substances 0.000 abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 abstract description 13
- 238000004061 bleaching Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004042 decolorization Methods 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 description 14
- 239000007844 bleaching agent Substances 0.000 description 11
- 238000005660 chlorination reaction Methods 0.000 description 9
- 238000011160 research Methods 0.000 description 8
- 229920001131 Pulp (paper) Polymers 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910000464 lead oxide Inorganic materials 0.000 description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical class OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 1
- TZALXFCHDRHZMO-UHFFFAOYSA-N 2-chloro-6-methoxyphenol Chemical compound COC1=CC=CC(Cl)=C1O TZALXFCHDRHZMO-UHFFFAOYSA-N 0.000 description 1
- GQKDZDYQXPOXEM-UHFFFAOYSA-N 3-chlorocatechol Chemical compound OC1=CC=CC(Cl)=C1O GQKDZDYQXPOXEM-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- -1 chloro vanillic aldehyde Chemical compound 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
本发明涉及一种氯化木素及其衍生物的降解方法，其采用电氧化降解法，将阳极和阴极插入含氯化木素及其衍生物的废水中，阳极与阴极的间距为0.2～1毫米之间，采用直流电，控制电解电压不高于水的电解电压进行电氧化处理。本发明具有技术设备小，占地少，运行管理简单，COD去除率高、脱色效果好等特点。尤其可用于纸浆含氯漂白废水中氯化木素及其衍生物的降解。The invention relates to a degradation method of chlorinated lignin and its derivatives, which adopts an electro-oxidative degradation method, inserts an anode and a cathode into wastewater containing chlorinated lignin and its derivatives, and the distance between the anode and the cathode is 0.2- Between 1 mm, direct current is used to control the electrolysis voltage not higher than the electrolysis voltage of water for electro-oxidation treatment. The invention has the characteristics of small technical equipment, less land occupation, simple operation and management, high COD removal rate, good decolorization effect and the like. It can be especially used for the degradation of chlorinated lignin and its derivatives in pulp chlorine bleaching wastewater.
Description
The present invention relates to the biodegrading process of a kind of chlorinated lignin and derivative thereof, especially can be used for the biodegrading process of chlorinated lignin in the paper pulp chlorine bleach waste water and derivative thereof.
What the pulp-making waste-water pollution was the most serious is chlorine bleach waste water, it not only shows on the problem of biological oxygen demand (BOD) (BOD) and chemical oxygen consumption (COC) (COD), and more seriously show and contain violent in toxicity (total organic chloride in the chlorine bleach waste water, Totalorganically-bond chlorine is called for short ' TOCl ') problem on.Paper chlorination and alkali treatment have the chloroform of carcinogenesis the mankind except producing, and also have many hypertoxic organic chloride deposits yields.They all are the chlorides of lignin degradation product, most forms with various chlorinated phenols exist, wherein based on dichloro-phenol, three chlorinated phenols, four chlorinated phenols, pentachloro-phenol, secondly, also have chloro guaiacol, chloro vanillic aldehyde, chloro catechol etc., they all are toxic pollutants, and difficult biochemistry and non-biochemical degradation, all are poisonous to fish and mammal.Therefore, chlorinated lignin in the paper pulp chlorine bleach waste water and derivative thereof are the main causes that pollutes.
Although a large amount of chlorine-free bleaching technology is in continuous research and extension, because popularity and the cost of chlorine-free bleaching technology and the limitation of technological requirement that the chlorine bleach technology is used, to such an extent as to the chlorine bleach technology is still in a large amount of uses.The research of relevant paper pulp chlorine bleach method for treating wastewater has microbial method, active dirty mud method etc., but these methods are because of the not extensive use greatly of long processing period, floor space, so far, paper pulp chlorine bleach waste water does not still have effective control measures, majority is the directly discharging of dilution back, and environment is caused great harm.
Electrochemical oxidation method has been widely used in numerous areas, as plating, electrolysis, battery etc., also is applied to organic synthetic and decomposition.The existing many reports of the electroxidation research of lignin, these researchs relate to functional group modification, halogenation and bleaching and the wastewater treatment of lignin.The research report of wherein bleaching aspect all is about adopting electroxidation method bleached pulp.The research of wastewater treatment aspect mainly is about handling the research of black digestion liquid.But utilizing the electroxidation method to handle has the research of chlorinated lignin in the chlorine bleach waste water not appear in the newspapers.
The method that the purpose of this invention is to provide a kind of Electrooxidation degradation chlorinated lignin and derivative thereof, its equipment that possesses skills is little, takes up an area of to lack, and operational management is simple, characteristics such as COD clearance height, good decolorizing effect.
The invention provides the Electrooxidation degradation method of chlorinated lignin and derivative thereof, its specific operation process comprises: anode and negative electrode insertion are contained in the waste water of chlorination lignin and derivative thereof, the spacing of anode and negative electrode is between 0.2～1 millimeter, adopt direct current, the decomposition voltage that the control decomposition voltage is not higher than water carries out the electroxidation processing.
Wherein the spacing of anode and negative electrode is between 0.2～1 millimeter, and the spacing of anode and negative electrode is more little, and the electroxidation treatment effect is good more, is preferably 0.2～0.5 millimeter.
The control decomposition voltage is not higher than the decomposition voltage of water, could carry out the Electrooxidation degradation effect effectively, and within this, decomposition voltage is high more, and effect is good more.Potential difference is big more between anode and the negative electrode, and the decomposition voltage of water raises, and the decomposition voltage of Electrooxidation degradation chlorinated lignin and derivative thereof is corresponding can be improved, and the electroxidation treatment effect is good more.
Usually should select resistance to oxidation, the higher anode material of oxygen evolution potential as far as possible,, consider, can take to plate on the carbon-point resistance to oxidation and the higher material of oxygen evolution potential and make anode, as plating brown lead oxide etc. from economic angle as precious metal nickel, platinum etc.Negative electrode does not have special requirement, and common cathode material can be suitable for, as stainless steel, copper etc.
The spacing of anode of the present invention and negative electrode is less, is between 0.2～1 millimeter, and the centre can adopt the insulation net to separate.
The present invention is particularly useful for the degraded of chlorinated lignin in the paper pulp chlorine bleach waste water and derivative thereof.
The present invention is to containing the bleaching effluent electrolysis of chlorination lignin and derivative thereof, can impel chlorinated lignin and derivative degraded thereof in the waste water, and ring-opening reaction takes place simultaneously, the infrared spectrum before and after containing chlorination lignin and derivative wastewater electrolytic thereof as can be seen.
Accompanying drawing is the infrared spectrum of waste water before and after decomposition voltage was handled for the 4.1V electroxidation 18 hours that contains the chlorination lignin.Before electrolysis, tangible aromatic ring characteristic absorption peak is arranged in the spectrogram, be 1600cm as wave number among the figure
-1Peak 1 be that aromatic ring vibration produces, wave number is 1147cm
-1 Peak 3 and wave number be 1043cm
-1Peak 4 be to produce by C-H plane deformation on the aromatic ring.And these peaks are 1565cm by wave number after the electrolysis
-1Peak 2 and wave number are 1112cm
-1Weak and wide peak 5 substitutes.As seen the characteristic absorption peak of aromatic ring becomes very weak after electrolysis, and this shows that electrolysis makes chlorinated lignin that ring-opening reaction take place.Can significantly reduce the various chlorinated phenols that form in the chlorinated lignin degradation process by ring-opening reaction, when reducing chroma in waste water and COD, effectively suppress the generation of huge malicious pollutant.Electroxidation is handled chlorine bleach waste water and is had the advantage that the cycle is short, cost is low, floor space is few.
Adopt electrochemical techniques to handle bleaching effluent and have many advantages, making oxidant or reductant with electronics replaces chemical example to carry out chemical reaction can saving preliminary treatment or post processing, utilize the variation of electric current and voltage to be easy to control reaction speed and type simultaneously, can operate under the normal temperature and pressure.Electrochemical techniques equipment is little, takes up an area of to lack, and operational management is simple, and COD clearance height, good decolorizing effect have good practical prospect.
Adopting a kind of lead dioxide electrode in the embodiment of the invention is anode, it is by being anode with the carbon-point, stainless (steel) wire is that negative electrode is at room temperature electroplated and obtained, electroplate liquid is 20% the lead acetate and the Schweinfurt green aqueous solution (adding Schweinfurt green is to be to increase electrical conductivity) for the quality percentage composition, and current density is 10～20mA/cm
2, electroplating time is 2～3 hours; Stainless (steel) wire is a negative electrode; The electrolytic tank of Zu Chenging is 100mA/cm in current density thus
2The time, the decomposition voltage of water is 4.129 volts, and decomposition voltage is controlled at 3～4 volts of comparatively ideals; The direct current that is adopted is a power supply with industrial alternating current, by voltage stabilizing, rectification, filtering, alternating current is become direct current, the bleaching effluent that contains the chlorination lignin is carried out electroxidation handle.
With the brown lead oxide bar electrode is anode, stainless (steel) wire is a negative electrode, electrolysis contains that chlorination lignin 0.1377g/l, colourity are 7444.4, COD is the bleaching effluent of 2445mg/l, when decomposition voltage is 2.9V, after the electrolysis 18 hours, chlorinated lignin concentration is that 0.0709g/l, colourity are 3141.4, COD is 1515.9mg/l.The chlorinated lignin rate of descent is 48.5%, the colourity rate of descent is 57.8%, the COD rate of descent is 38%.
With the brown lead oxide bar electrode is anode, stainless (steel) wire is a negative electrode, electrolysis contains that chlorination lignin 0.1459g/l, colourity are 4697, COD is the bleaching effluent of 2399.5mg/l, when decomposition voltage is 3.3V, after the electrolysis 18 hours, chlorinated lignin concentration is that 0.0745g/l, colourity are 1727.3, COD is 1214.5mg/l.The chlorinated lignin rate of descent is 48.9%, the colourity rate of descent is 63.2%, the COD rate of descent is 49.4%.
With the brown lead oxide bar electrode is anode, stainless (steel) wire is a negative electrode, electrolysis contains that chlorination lignin 0.1632g/l, colourity are 8575.8, COD is the bleaching effluent of 3683.7mg/l, when decomposition voltage is 4.1V, after the electrolysis 18 hours, chlorinated lignin concentration is that 0.0259g/l, colourity are 742, COD is 1030.4mg/l.The chlorinated lignin rate of descent is 84.1%, the colourity rate of descent is 91.3%, the COD rate of descent is 72%.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00130810A CN1095514C (en) | 2000-11-22 | 2000-11-22 | Process for degradating chlorinated lignin and its derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00130810A CN1095514C (en) | 2000-11-22 | 2000-11-22 | Process for degradating chlorinated lignin and its derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1305030A CN1305030A (en) | 2001-07-25 |
| CN1095514C true CN1095514C (en) | 2002-12-04 |
Family
ID=4594315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00130810A Expired - Fee Related CN1095514C (en) | 2000-11-22 | 2000-11-22 | Process for degradating chlorinated lignin and its derivatives |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1095514C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962449A (en) * | 2010-08-26 | 2011-02-02 | 中国农业大学 | Method for removing lignin from biomass by using alkaline electrolyzed functional water |
| CN102277591A (en) * | 2011-08-02 | 2011-12-14 | 北京化工大学 | Method for electrochemically degrading lignin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5061643A (en) * | 1989-03-30 | 1991-10-29 | Mitsubishi Denki Kabushiki Kaisha | Method of doping a growing crystalline semiconductor film |
| CN1153843A (en) * | 1996-09-10 | 1997-07-09 | 刘友会 | Alkali process for treating black liquor |
| CN1162664A (en) * | 1996-04-13 | 1997-10-22 | 刘相才 | Method for both pulp producing and papermaking |
-
2000
- 2000-11-22 CN CN00130810A patent/CN1095514C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5061643A (en) * | 1989-03-30 | 1991-10-29 | Mitsubishi Denki Kabushiki Kaisha | Method of doping a growing crystalline semiconductor film |
| CN1162664A (en) * | 1996-04-13 | 1997-10-22 | 刘相才 | Method for both pulp producing and papermaking |
| CN1153843A (en) * | 1996-09-10 | 1997-07-09 | 刘友会 | Alkali process for treating black liquor |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962449A (en) * | 2010-08-26 | 2011-02-02 | 中国农业大学 | Method for removing lignin from biomass by using alkaline electrolyzed functional water |
| CN101962449B (en) * | 2010-08-26 | 2012-11-14 | 中国农业大学 | Method for removing lignin from biomass by using alkaline electrolyzed functional water |
| CN102277591A (en) * | 2011-08-02 | 2011-12-14 | 北京化工大学 | Method for electrochemically degrading lignin |
| CN102277591B (en) * | 2011-08-02 | 2014-03-05 | 北京化工大学 | A method for electrochemically degrading lignin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1305030A (en) | 2001-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Malpass et al. | Recent advances on the use of active anodes in environmental electrochemistry | |
| Köktaş et al. | Tetracycline removal from aqueous solution by electrooxidation using ruthenium-coated graphite anode | |
| Chiang et al. | Indirect oxidation effect in electrochemical oxidation treatment of landfill leachate | |
| Rajkumar et al. | Electrochemical treatment of industrial wastewater | |
| Can | COD removal from fruit-juice production wastewater by electrooxidation electrocoagulation and electro-Fenton processes | |
| CN101555082B (en) | Waste water treatment method and device combining electrochemical degradation and photocatalytic oxidation technologies | |
| Yu et al. | Electrocatalytic degradation of sulfamethazine on IrO2-RuO2 composite electrodes: influencing factors, kinetics and modeling | |
| CN107117690A (en) | Electrocatalytic oxidation handles the device and method of Recalcitrant chemicals | |
| US20020153245A1 (en) | Flow-through eletrochemical reactor for wastewater treatment | |
| CN111115761A (en) | An electrochemical reaction device and method for synchronously removing total nitrogen in electroplating wastewater | |
| US6908541B2 (en) | Electrolytic catalytic oxidation system | |
| CN105016431A (en) | Method and apparatus for removal and recovering of heavy metal ions from wastewater | |
| US20250136481A1 (en) | Anode and cathode synergistic electrocatalytic system for wastewater treatment and application | |
| Zhang et al. | Anodic treatment of acrylic fiber manufacturing wastewater with boron-doped diamond electrode: a statistical approach | |
| AU652341B2 (en) | Process for treatment of water and apparatus therefor | |
| Wang et al. | Environmental risk control of florfenicol in water: From technology selection to mechanism discussion | |
| CN1095514C (en) | Process for degradating chlorinated lignin and its derivatives | |
| Soloman et al. | Electrochemical degradation of pulp and paper industry waste‐water | |
| US4834852A (en) | Process for the activation of hydrogen peroxide | |
| CN1962471A (en) | Method for electrolyzing organic waste water using iridium tantalum stannum oxide coating titanium electrode | |
| CN1232446C (en) | Method and apparatus for treating water by catalytic reduction of nano metal-memebrane composite electrode | |
| Tang et al. | A review of electrochemical treatment processes of leachate membrane concentrate | |
| Li et al. | Optimization of electrolytic system type for industrial reverse osmosis concentrate treatment to achieve effluent quality and energy savings | |
| CN214880416U (en) | Three-dimensional electro-catalytic treatment device | |
| JPH1110160A (en) | Method for treating water by electrolytic oxidation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |