CN101491726A - Dioxins inhibitor and manufacturing method thereof - Google Patents
Dioxins inhibitor and manufacturing method thereof Download PDFInfo
- Publication number
- CN101491726A CN101491726A CN 200810003583 CN200810003583A CN101491726A CN 101491726 A CN101491726 A CN 101491726A CN 200810003583 CN200810003583 CN 200810003583 CN 200810003583 A CN200810003583 A CN 200810003583A CN 101491726 A CN101491726 A CN 101491726A
- Authority
- CN
- China
- Prior art keywords
- inhibitor
- dioxins
- oxide
- iron
- calcium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Fire-Extinguishing Compositions (AREA)
Abstract
The invention discloses a dioxin inhibitor, which is prepared from rubber pyrolysis oil and a metallic oxide, wherein the rubber pyrolysis oil is produced through the thermal cracking of tires and contains 0.5 to 1.5 percent of sulfur, and the metallic oxide is an oxide of iron, an oxide of calcium or a mixture of the oxide of iron and the oxide of calcium. Taking the weight of the inhibitor in a dry state as a reference, the inhibitor comprises 1 to 5 weight percent of sulfur, 10 to 35 weight percent of iron and 0.5 to 1.5 weight percent of calcium.
Description
Technical field
The present invention relates to a kind of dioxins inhibitor, relate in particular to a kind of by prepared dioxins inhibitor and the manufacture method thereof of rubber cracking oil.
Background technology
Along with the progress in epoch, relative, the air-polluting problem is serious day by day, and national governments there's no one who doesn't or isn't rack one's brains and make every effort to improve, and along with the increasingly stringent of environmental requirement, industrial quarters needs more urgent to effective control air-polluting.
As everyone knows, harmful material in the general air pollution probably can be divided into volatile organic solvent (VOC) discarded object, nitrogen oxide (NOx) and dioxin (Dioxin) etc.
Wherein, because dioxin has anxious toxicity to organism, and can constantly accumulate in body, " poison in century " is otherwise known as.Dioxin mainly is to be present in urban waste, trade waste or the Biohazard Waste that contains the chlorine polymer, in incineration course, though under high-temperature operation, the burning product dioxin of rubbish or discarded object can be decomposed, but also may have part dioxin residue, or the dioxin that in temperature-fall period, had originally decomposed again polymerization form dioxin.
Please refer to Fig. 1, it is the formation mechanism schematic diagram of known dioxin.Wherein, as shown in the figure, discarded object 1 may produce straight chain hydrocarbon compound 20 and aromatic hydrocarbons 21 in the process of combustion reaction S101, also may part unburned carbon 22 also residually be arranged or directly generate dioxin 3.Then, straight chain hydrocarbon compound 20, aromatic hydrocarbons 21 and unburned carbon 22 can be respectively via cyclization S102, aminating reaction S103 and low temperature again synthetic reaction S104 form the aromatic hydrocarbons 23 of ammonification that is dioxin precursor 23.In addition, unburned carbon 22 also can via low temperature again synthetic reaction S104 directly generate dioxin 3.At last, the aromatic compound 23 of ammonification (being the dioxin precursor) forms dioxin 3 via the incorgruous catalytic reaction S106 of predecessor.
According to the formation mechanism of above-mentioned dioxin 3 can find in incineration course to produce dioxin dominant mechanism nothing more than High Temperature Gas be combined to, predecessor heterogeneous catalytic reaction and low temperature is synthetic again.The generation that therefore will reduce dioxin can stop the generation of its precursor and the dioxin that (2) removal has generated to be set about from (1).
Early stage employed processing method is exactly to utilize the adsorption capacity absorption dioxin of active carbon, and the method for use (active carbon adsorption) has basically: (1) ADSORPTION IN A FIXED BED method (Fixed-bed Filters); (2) active carbon insufflation (Carbon Injection) dual mode, when adopting the active carbon insufflation, the dry type shot-like particle collecting devices such as whirlwind dust collector, bag filter precipitron or electrostatic precipitation machine of must arranging in pairs or groups; If the shot-like particle dust collect plant of incinerator is a wet processed equipment, adopt the active carbon insufflation, will cause the packed layer of wet scrubbing tower or the obstruction of demister (De-mister), and influence the normal running of incineration system.In addition, the shortcoming of active carbon adsorption is only the dioxin in the gas phase to be transferred in the active carbon, and can't really decompose the destruction dioxin.Therefore, if do not deal carefully with the active carbon that contains dioxin, for example bury waste active carbon after, also might soak leakage via phreatic, via getting back to after the plant absorbing on the food chain, the final still quilt mankind absorb and influence human beings'health, environment are also had the danger of the secondary pollution of causing again.Moreover at present the active carbon price is expensive day by day, and the practitioner reduces use amount in order to save cost as far as possible, remote-effects check the effect of incinerator discharging dioxin amount.
As for other processing method, such as: the catalyst oxidizing process and the thermal decomposition method etc. of burning again, have the treatment system costliness too, do not meet financial cost, maybe need expend shortcomings such as a large amount of energy.
In sum, at present known variously prevent and treat method and fail to reach desirable condition, remain disadvantages, as: the dioxin treatment effect is not good, the required fund of updating the equipment is huge, handle with the raw material costliness etc., all waits to improve.Taiwan, Japan build a large amount of incinerators in order to handle discarded object now, and the dioxin total amount of discharging every day is quite surprising, so in order to take into account above-mentioned all considerations simultaneously, how to improve existing dioxin control technology and face very acid test.
In view of this, in order effectively to address the above problem, the inventor urgently thinks the method that suppresses or get rid of dioxin in improving invariably, beyond expectation can be found a kind of dioxin inhibition method of saving former material cost, also must meet the requirement of environmental protection new regulation now.
Because " environmental protection " is the emphasis of global evolution already, the new concept of discarded object being regarded as resource is not only introduced in Taiwan in recent years, has more formulated the relevant laws and regulations order based on environmental protection Basic Law relevant regulations.
Wherein, fast development along with auto industry and highway communication transport service, demand to various tires also increases day by day all over the world, the year sales volume of world's tire reaches tens00000000 at present, and each automotive average travels 30,000 to 50,000 kilometers just must change a tire, causes the situation of tire year learies in the world's up to 10,000,000 tons.Therefore, the comprehensive utilization of old tire more and more is subjected to people's attention, because this is the effective way that reduces environmental pollution, turns waste into wealth.
Summary of the invention
For solving the problems of the technologies described above, main purpose of the present invention is to provide a kind of dioxins inhibitor (Dioxin inhibitor) that is formed by rubber cracking oil and metal oxide modulation, when obtaining effectively to suppress the inhibitor of dioxin generation, realize utilization again to rubber such as waste tires.
The present invention also aims to provide the preparation method of above-mentioned dioxins inhibitor, obtain rubber cracking oil, and mix the metal oxide acquisition dioxin is suppressed the good dioxins inhibitor of effect by waste tire being carried out thermal cracking.
For achieving the above object, the invention provides a kind of dioxins inhibitor, it is to form with rubber cracking oil and metal oxide modulation.
According to concrete scheme of the present invention, described rubber cracking oil can be (promptly this rubber cracking oil is tire pyrolysis oil) of utilizing the hot cracked reaction of the damaged tire that reclaims to generate, and contains the sulphur of 0.5% to 1.5% weight.Described metal oxide can be that the oxide of oxide, calcium of iron or its mix, and its optional autoxidation is ferrous, one or more the mixing in di-iron trioxide, tri-iron tetroxide, calcium oxide and the calper calcium peroxide etc.
In the dioxins inhibitor provided by the invention, described metal oxide can be selected the oxide from iron, oxide or its mixing of calcium.In addition, be benchmark with the weight of this inhibitor when the drying regime, wherein can comprise the sulphur of 1 to 5 percentage by weight, the iron of 10 to 35 percentage by weights and the calcium of 0.5 to 1.5 percentage by weight.Though the content of described sulphur, iron and calcium is in constituent content, their existence or interpolations in inhibitor are not restricted to simple substance.
The present invention also provides the manufacture method of above-mentioned dioxins inhibitor, and its step comprises: rubber is carried out heat scission reaction to produce rubber cracking oil; And, mix at least a metal oxide to cracked oil, mix forming inhibitor.
According to concrete technical scheme of the present invention, in the manufacture method of dioxins inhibitor, the rubber cracking oil that is adopted is by carrying out the heat scission reaction preparation to tire; This rubber cracking oil can contain the sulphur of 0.5% to 1.5% weight.The metal oxide that is adopted can be that the oxide of oxide, calcium of iron or its mix, and its optional autoxidation is ferrous, one or more the mixing in di-iron trioxide, tri-iron tetroxide, calcium oxide and the calper calcium peroxide etc.
In the manufacture process of inhibitor, mix metal oxide to rubber cracking oil the time, make the mixed ratio of sulphur, iron and calcium be respectively 1 to 5 percentage by weight, 10 to 35 percentage by weights and 0.5 to 1.5 percentage by weight of described inhibitor weight when drying regime.
Dioxins inhibitor provided by the invention; its raw material sources---cracked oil; can use bulk deposition and easily cause the waste tire of environmental pollution, thereby realize resource, the harmless treatment of waste tire, meet the notion and the specification requirement of environmental protection now and sustainable development fully.
The use of dioxins inhibitor provided by the invention does not need expensive treating apparatus, can reduce known use catalyst oxidizing process and the thermal decomposition method of burning is again taken high financial cost and huge energy consumption problem handling on the dioxin.
Cracked oil of the present invention is the higher rubber cracking oil of sulfur content, only needs a spot of cracked oil can modulate inhibitor, has reached cost-effective purpose.And when dioxins inhibitor of the present invention was sprayed on the chlorine-containing waste of desire burning, its consumption only was 0.001 to 0.1 of a waste-material dry basic weight amount, therefore, only need provide a spot of dioxins inhibitor just can suppress the generation of dioxin effectively.
Comprehensive the above, dioxins inhibitor provided by the present invention can not only suppress the generation of dioxin effectively, and enforcement of the present invention has further realized resource, the harmless treatment of waste tire.
Description of drawings
Fig. 1 is the schematic diagram of known dioxin formation mechanism;
Fig. 2 utilizes inhibitor of the present invention to realize suppressing the chemical equation that dioxin generates;
Fig. 3 is the schematic flow sheet of the dioxins inhibitor manufacture method of the embodiment of the invention;
Fig. 4 is the schematic flow sheet of the dioxins inhibitor using method of the embodiment of the invention.
The primary clustering symbol description:
1 discarded object
20 direct steel hydrocarbons
21 aromatic hydrocarbonses
22 unburned carbons
23 ammonification aromatic hydrocarbonses (dioxin precursor)
The 23a chlorobenzene
The 23b chlorophenol
The compound of 23 ' the non-dioxin state
3 dioxins
4 dioxins inhibitors
40 sulphur
41 di-iron trioxides
42 calcium oxide
The accessory substance of 5 dechlorination reactions
S101-S106 dioxin formation mechanism
The S101 combustion reaction
The S102 cyclization
The S103 aminating reaction
S104 low temperature is synthetic reaction again
S105 directly generates
The incorgruous catalytic reaction of S106 predecessor
The manufacturing process of S201-S204 dioxins inhibitor
The use flow process of S301-S303 dioxins inhibitor
The specific embodiment
About the advantages and spirit of the present invention, and more detailed embodiment can be by following embodiment and appended graphic being further understood.
Please refer to Fig. 2, it has shown the chemical equation that utilizes inhibitor of the present invention to realize suppressing the dioxin generation, the discharge capacity of dioxin 3 when incinerating for adopting the generation that stops dioxin precursor (being the ammonification aromatic hydrocarbons) 23 to reduce.
As shown in the figure, when inhibitors 4 is subjected to pyrolytic, will be with SO
XThe chlorine atom that functional group displacement dioxin precursor 23 is contained carries out dechlorination reaction (Dechlorination Reaction), forms the compound 23 ' (being the aromatic series sulfur compound) of the lower non-dioxin state of nonpoisonous state or toxicity.Wherein, dioxin precursor 23 can be chlorobenzene (monochlorobenzene, MCB) 23a, chlorophenol (for example 2-chlorophenol (2-monochlorophenol, MCP)) 23b or its mixing.In addition, still accessory substance 5 be can produce after the reaction, iron chloride, calcium chloride and water etc. included.
Then, please refer to Fig. 3, it has shown the schematic flow sheet of manufacture method of the dioxins inhibitor 4 of the embodiment of the invention.As shown in the figure, the manufacture method of a kind of dioxins inhibitor provided by the present invention, its step comprises: at first rubber is carried out heat scission reaction S201, to produce rubber cracking oil S202.Then, mix metal oxide S203 to this rubber cracking oil, and stir to make it fully to mix and form dioxins inhibitor S204.Wherein, described rubber is tire, for example is the discarded tire that reclaims.And metal oxide is a di-iron trioxide 41 and the mixing of calcium oxide 42, yet it only is a preferred embodiment, and metal oxide used in the present invention is not limited in this, precedingly states clearly.
What further specify is, rubber is carried out the rubber cracking oil of heat scission reaction gained by the present invention, its sulfur content is 0.5% to 1.5% weight, in preferred embodiment, sulfur content is between 0.9%-1.2%, sulfur content compared at present general heavy oil is 0.1%, and rubber cracking oil of the present invention contains higher sulphur composition.
In preferred embodiment, above-mentioned is the low temperature heat scission reaction to the rubber heat scission reaction, and wherein the range of reaction temperature of this heat scission reaction is between 300 to 500 ℃.It should be noted that, the cracking technique that general damaged tire recovery is adopted is the Pintsch process with about 1000 ℃, because the organic waste thermal conductance is very low, the discarded object heating must be reached 550 ℃ of-600 ℃ of ability cracking at least and finish, so heat temperature raising is chronic, treating capacity is difficult for enlarging.In addition, because high-temperature process, cracked oil also is easy to vaporization and influences actual oil pump capacity.Handle rubber to obtain a large amount of and stable rubber cracking oil so adopt the low temperature heat scission reaction in the preferred embodiment of the present invention.Yet this is preferred embodiment of the present invention only, and the present invention is not limited to this, can not even if use high temperature pyrolysis to react to handle rubber also not have.
Moreover what need to specify is, the content of sulphur 40, iron, calcium preferably is respectively 1 to 5 percentage by weight, 10 to 35 percentage by weights and 0.5 to 1.5 percentage by weight in the weight of this inhibitors 4 when the drying regime in the inhibitors 4.
According to above description, just can know composition, proportion of composing and the manufacture method thereof of understanding dioxins inhibitor provided by the invention, and the occupation mode of this dioxins inhibitor can be with further reference to the schematic flow sheet of Fig. 4.
Please refer to Fig. 4, the schematic flow sheet of the dioxins inhibitor using method that it provides for embodiments of the invention.Its using method comprises the following steps: at first, and dioxins inhibitor S301 is provided, and its relevant manufacture method provides in preamble, does not repeat them here.
Then, inhibitor is interspersed among S302 on the chlorine-containing waste of desire burning.Wherein, inhibitor is that the amount in 0.001 to 0.1 ratio of waste-material dry basic weight amount intersperses among on the discarded object, and the mode of its distribution can select blowing to spill, splash or soak into, and is not limited to above-mentioned arbitrary mode for it.Subsequently, burning is with the discarded object S303 of inhibitor.Wherein, be that environment at least 800 ℃ or higher temperature carries out combustion reaction with the discarded object of inhibitor, the effect that inhibitor produced is the most remarkable.Yet this environment for use temperature only is a preferred embodiment, and the environment for use of dioxins inhibitor of the present invention is not limited to this, also can produce the effect that suppresses dioxin.
In sum, can understand that dioxins inhibitor provided by the present invention and manufacture method thereof have following advantage:
(1) dioxins inhibitor among the present invention; its raw material sources---cracked oil; be to use bulk deposition and easily cause the waste tire of environmental pollution, realized resource, the harmless treatment of waste tire, meet the notion and the specification requirement of environmental protection now and sustainable development fully.
(2) hold above-mentionedly,, can significantly reduce cost of material just because of technical scheme of the present invention is to utilize at waste tire again.In addition, cracked oil mixed with metal oxide be sprayed on again on the discarded object, the treating apparatus that does not also need costliness also can reduce known use catalyst oxidizing process and the thermal decomposition method of burning is again taken high financial cost and huge energy consumption problem on the processing dioxin.Moreover, compared to known use active carbon adsorption, there is not follow-up secondary pollution problem yet, see that really the present invention can effectively solve the problem that is faced on the known skill.
(3) more as mentioned before, cracked oil prepared in accordance with the present invention, its sulfur content is 0.5% to 1.5% weight, is the higher cracked oil of sulfur content, meaning promptly only needs a spot of cracked oil can modulate inhibitor, has reached cost-effective purpose.
(4), when dioxins inhibitor of the present invention is sprayed on the chlorine-containing waste of desire burning, be to intersperse among on the discarded object with respect to discarded object ratio of 0.001 to 0.1 of weight when the drying regime according to the step S302 of aforementioned using method.Therefore, only need provide a spot of dioxins inhibitor just can suppress the generation of dioxin effectively, relatively also reach cost-effective purpose.
Though the present invention illustrates as above with preferred embodiments, so it is not only to terminate in the foregoing description in order to limit the present invention's spirit with the invention entity.The technical staff in the technical field is when understanding and utilize other assembly or mode to produce identical effect easily.Be with, the modification of being done in not breaking away from spirit of the present invention and scope all should be included in the claim scope of the present invention.
Claims (10)
1. a dioxins inhibitor is to form with rubber cracking oil and metal oxide modulation.
2. dioxins inhibitor as claimed in claim 1, wherein, described rubber cracking oil is tire pyrolysis oil.
3. dioxins inhibitor as claimed in claim 1, wherein, described rubber cracking oil contains the sulphur of 0.5% to 1.5% weight.
4. as claim 1 or 3 described dioxins inhibitors, wherein, described metal oxide is that the oxide of oxide, calcium of iron or its mix, and it is selected from one or more the mixing in ferrous oxide, di-iron trioxide, tri-iron tetroxide, calcium oxide and the calper calcium peroxide.
5. dioxins inhibitor as claimed in claim 4 wherein, is a benchmark with the weight of this inhibitor when the drying regime, wherein comprises the sulphur of 1 to 5 percentage by weight, the iron of 10 to 35 percentage by weights and the calcium of 0.5 to 1.5 percentage by weight.
6. the manufacture method of a dioxins inhibitor, its step comprises:
Rubber is carried out heat scission reaction with preparation rubber cracking oil; And
Mix at least a metal oxide to this rubber cracking oil, mix forming inhibitor.
7. the manufacture method of dioxins inhibitor as claimed in claim 6, wherein, described rubber cracking oil is by carrying out the heat scission reaction preparation to tire.
8. the manufacture method of dioxins inhibitor as claimed in claim 6, wherein, described rubber cracking oil contains the sulphur of 0.5% to 1.5% weight.
9. the manufacture method of dioxins inhibitor as claimed in claim 8, wherein, described metal oxide is that the oxide of oxide, calcium of iron or its mix, and it is selected from one or more the mixing in ferrous oxide, di-iron trioxide, tri-iron tetroxide, calcium oxide and the calper calcium peroxide.
10. the manufacture method of dioxins inhibitor as claimed in claim 9, wherein, mix the step of at least a metal oxide to the rubber cracking oil, make the mixed ratio of sulphur, iron and calcium be respectively 1 to 5 percentage by weight, 10 to 35 percentage by weights and 0.5 to 1.5 percentage by weight of described inhibitor weight when drying regime.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810003583 CN101491726B (en) | 2008-01-25 | 2008-01-25 | Dioxins inhibitor and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810003583 CN101491726B (en) | 2008-01-25 | 2008-01-25 | Dioxins inhibitor and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101491726A true CN101491726A (en) | 2009-07-29 |
| CN101491726B CN101491726B (en) | 2013-02-20 |
Family
ID=40922624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810003583 Expired - Fee Related CN101491726B (en) | 2008-01-25 | 2008-01-25 | Dioxins inhibitor and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101491726B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4745226A (en) * | 1986-09-22 | 1988-05-17 | Stauffer Chemical Company | Reaction of sulfur with polychlorinated polyphenyls |
| JPH0685806B2 (en) * | 1987-08-11 | 1994-11-02 | 米澤化学工業株式会社 | Method for detoxifying organic halogen compounds |
| TW200402316A (en) * | 2002-08-07 | 2004-02-16 | Miura Kogyo Kk | Soil treatment agent and soil treating method |
| CN1850371A (en) * | 2006-06-02 | 2006-10-25 | 清华大学 | Micro-wave heating desorption/alkyl catalytic decomposition treatment method for polychlorinated biphenyl in soil |
-
2008
- 2008-01-25 CN CN 200810003583 patent/CN101491726B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101491726B (en) | 2013-02-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cudjoe et al. | Environmental impact analysis of municipal solid waste incineration in African countries | |
| CN103721550B (en) | Flue gas and desulfurizing and denitrifying takes off VOCs absorbent and preparation thereof and application | |
| CN102068890B (en) | Method and device for treating complex industrial organic waste gas | |
| CN105841168A (en) | Integrated treatment method for malodorous VOCs gas of refining devices | |
| CN206577577U (en) | A kind of cleaning system for municipal sewage plant's domestic sludge incineration flue gas | |
| CN101024162A (en) | Organic waste-gas adsorbant and preparing method and use | |
| CN107469506A (en) | The method and device of low temperature plasma pyrolysis oxidization reactor for treatment foul waste gas | |
| TW201726230A (en) | Methods and systems for particulate matter removal from a process exhaust gas stream | |
| WO2019062350A1 (en) | Harmless treatment method and system for domestic sludge | |
| CN106731486A (en) | A kind of petrifaction sewage Treatment stations discharge the integrated conduct method and device of waste gas | |
| Chen et al. | Environment pollutants removal with non-thermal plasma technology | |
| Zhai et al. | Potential reuse options for biomass combustion ash as affected by the persistent organic pollutants (POPs) content | |
| CN101491726B (en) | Dioxins inhibitor and manufacturing method thereof | |
| CN103398386A (en) | Device and method for disposing sludge based on chemical looping combustion | |
| Wang et al. | Inhibition behavior of PCDD/fs congeners by addition of N-containing compound in the iron ore sintering | |
| Zhao et al. | Analysis and discussion on formation and control of dioxins generated from municipal solid waste incineration process | |
| Wu et al. | A typical 300 MW ultralow emission coal-fired power plant: Source, distribution, emission, and control of polycyclic aromatic hydrocarbons | |
| CN111765479A (en) | Process method for effectively inhibiting dioxin in solid waste incineration flue gas | |
| CN101322905B (en) | Method for purifying and processing cement revolving tubular kiln cooperated with consumer waste incineration flue gas | |
| Zhuang et al. | Analysis on comprehensive treatment of VOCs in key industries of a city | |
| CN113894136B (en) | Method for removing TOC (total organic carbon) in industrial solid waste salt | |
| CN113860265B (en) | System and process for preparing sulfur by efficiently treating alkylated waste acid | |
| Zhang et al. | Federal Air Pollutant Emission Regulations and Preliminary Estimates of Potential-to-Emit from Biorefineries. Pathway# 1: Dilute-Acid and Enzymatic Deconstruction of Biomass-to-Sugars and Biological Conversion of Sugars-to-Hydrocarbons | |
| CN105327609A (en) | Treating agent for removing three kinds of dioxin-like compounds in waste incineration waste off gas | |
| Urbaniak | Waste to Products: Hydrothermal Carbonization and Activation of Sewage Sludge for a Circular Economy Analyzed through a Whole Systems Perspective |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| 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: 20130220 Termination date: 20210125 |