CN103613225B - The combination treatment method of sulfur-containing waste water and Mn-bearing waste water - Google Patents
The combination treatment method of sulfur-containing waste water and Mn-bearing waste water Download PDFInfo
- Publication number
- CN103613225B CN103613225B CN201310648200.3A CN201310648200A CN103613225B CN 103613225 B CN103613225 B CN 103613225B CN 201310648200 A CN201310648200 A CN 201310648200A CN 103613225 B CN103613225 B CN 103613225B
- Authority
- CN
- China
- Prior art keywords
- waste water
- sulfur
- combination treatment
- inclined tube
- treatment method
- 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
Landscapes
- Removal Of Specific Substances (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides the combination treatment method of a kind of sulfur-containing waste water and Mn-bearing waste water.The method comprises: (1) vulcanization reaction: add sulfur-containing waste water in Mn-bearing waste water, stirring reaction, as [Mn in mixing solutions
2+] & lt; Stopped reaction during 1ppm, then solid-liquid separation, gained filtrate enters next step operation; (2) oxidation sweetening: Manganse Dioxide breeze particle volume diameter being less than 120 microns (crossing 120 mesh sieves), the filtrate obtained with step (1) vulcanization reaction is pulled an oar, and obtains slurry, then loads in inclined tube; And (3) solid-liquid separation: by the liquid solid-liquid separation obtained from inclined tube top, obtain manganese monoxide solid and reuse water.Combination treatment of the present invention sulfur-containing waste water and Mn-bearing waste water, obtain the raw material of reproducible utilization, reduce processing cost.
Description
Technical field
The present invention relates to domain of inorganic chemistry, concrete, relate to the combination treatment method of a kind of sulfur-containing waste water and Mn-bearing waste water.
Background technology
Barium strontium salt industry adopts reduction with carbon---leaching---process for carbonization production, containing sulfide and polysulfide in process recycled water and the infiltration of slag field.In addition, a certain amount of processing wastewater and the infiltration of slag field that contain mn ion is produced in electrolytic manganese dioxide production process.Original art treatment adopts hydrogen peroxide treatment sulfur-containing waste water, adopts lime treatment Mn-bearing waste water.These art treatments exist that processing cost is high, the quantity of slag is comparatively large, the inefficient problem of resource reclaim.
Summary of the invention
Technical problem to be solved by this invention is: processing cost is high respectively to overcome existing sulfur-containing waste water and Mn-bearing waste water, the inefficient defect of resource reclaim, provide the combination treatment method of a kind of sulfur-containing waste water and Mn-bearing waste water, obtain the raw material of reproducible utilization, reduce processing cost.
In order to solve the problems of the technologies described above, the first technical scheme provided by the invention is, the combination treatment method of a kind of sulfur-containing waste water and Mn-bearing waste water, and the method comprises:
(1) vulcanization reaction
Sulfur-containing waste water is added, stirring reaction, as [Mn in mixing solutions in Mn-bearing waste water
2+] <1ppm time stopped reaction, then solid-liquid separation, gained filtrate enter next step operation;
(2) oxidation sweetening
Particle volume diameter is less than the Manganse Dioxide breeze of 120 microns (crossing 120 mesh sieves), the filtrate obtained with step (1) vulcanization reaction is pulled an oar, and obtains slurry, then loads in inclined tube;
Described slurry enters from the bottom of inclined tube, then from inclined tube top fluid, controls described flow rate of slurry at 0.2m/h-0.25m/h; And
(3) solid-liquid separation
By the liquid solid-liquid separation obtained from inclined tube top, obtain manganese monoxide solid and reuse water.
The combination treatment method of aforesaid sulfur-containing waste water and Mn-bearing waste water, described Mn-bearing waste water is for containing the bivalent ions waste water of manganese, the waste water of preferred sulfur acid manganese.Waste water can be produced in electrolytic manganese dioxide production process, these waste water are the waste water containing manganese divalent ion (manganous sulfate), according to the difference producing operation, manganous sulfate concentration is different, such as, in electrolytic manganese dioxide chemical combination wash heat pulp water, a bit, electrolytic manganese dioxide rinse water and mill floor wash-down water manganese ion concentration can be lower for manganese ion concentration meeting height.But all bivalent ions waste water of manganese that contains all can be applicable to the present invention, not by the impact of Manganese in Waste Water ionic concn.
The combination treatment method of aforesaid sulfur-containing waste water and Mn-bearing waste water, described sulfur-containing waste water is the waste water containing barium sulphide and/or strontium sulfide.Barium strontium salt industry adopts reduction with carbon-leaching-process for carbonization production, and the compound of sulfide (barium sulphide and/or strontium sulfide) and other sulfur-bearing is contained in process recycled water and slag field in seeping water, such as polysulfide.Preferably in described sulfur-containing waste water adds, add sodium sulphite, to maintain S
2-concentration is at 2.5-3.0g/L.
The combination treatment method of aforesaid sulfur-containing waste water and Mn-bearing waste water, in step (1), described solid-liquid separation gained filter cake reclaims manganese after sulfuric acid acidation, separation.Containing manganese sulfide and barium sulfate in solid-liquid separation gained filter cake, adopt sulfuric acid acidation, the manganese sulfide in filter cake is converted into solvable manganese salt, reaches the object reclaiming manganese.
The combination treatment method of aforesaid sulfur-containing waste water and Mn-bearing waste water, gained filter cake is after acidifying, being separated, and acidifying residue enters converter as the raw material preparing barium sulphide.After above-mentioned sulfuric acid acidation filter cake, barium sulfate remains in acidifying residue, is further used for preparing barium sulphide.
The combination treatment method of aforesaid sulfur-containing waste water and Mn-bearing waste water, in step (2), described inclined tube inclination 40-50 degree, preferably 45 degree.Inclined tube is of a size of ￠ (700-1000) × (4000-8000) mm, preferred ￠ 800 × 6000mm.The low top, bottom of inclined tube is high, and therefore slurry liquid level exports liquid level higher than inclined tube, utilizes this potential difference to save the energy, has carried out preliminary solid-liquid separation, thus can improve the utilising efficiency of manganese oxide.
The combination treatment method of aforesaid sulfur-containing waste water and Mn-bearing waste water, in step (2), described inclined tube is thtee-stage shiplock.Described thtee-stage shiplock refers to, the upper liquid outlet of a upper inclined tube connects the bottoms material entrance of next inclined tube, and three inclined tubes are from beginning to end successively, forms series connection.Slurry enters from the bottom of the first inclined tube, then from the first inclined tube top fluid, then enters the second inclined tube, the 3rd inclined tube successively, control described slurry in each inclined tube flow velocity at 0.2m/h-0.25m/h.
The combination treatment method of aforesaid sulfur-containing waste water and Mn-bearing waste water, in step (3), gained reuse water is as middle water circulation use.
Adopt technical scheme of the present invention, at least there is following beneficial effect:
Adopt vulcanization reaction-oxidation desulfuration process, combination treatment sulfur-containing waste water and Mn-bearing waste water, obtain the raw material of reproducible utilization, reduce processing cost.
Accompanying drawing explanation
The process flow sheet that Fig. 1 the present invention is main.
Embodiment
For fully understanding the object of the present invention, feature and effect, by following concrete embodiment, the present invention is elaborated.
Shown in composition graphs 1, the combination treatment method of a kind of sulfur-containing waste water and Mn-bearing waste water, the method comprises:
(1) vulcanization reaction
In Mn-bearing waste water, constantly add sulfur-containing waste water, stirring at normal temperature is reacted, as [Mn in mixing solutions
2+] <1ppm time stop add sulfur-containing waste water and termination reaction, then solid-liquid separation, gained filtrate enter next step operation.
Mn-bearing waste water is for containing the bivalent ions waste water of manganese, the waste water of preferred sulfur acid manganese.Waste water can be produced in electrolytic manganese dioxide production process, these waste water are the waste water containing manganese divalent ion (manganous sulfate), according to the difference producing operation, manganous sulfate concentration is different, such as, in electrolytic manganese dioxide chemical combination wash heat pulp water, a bit, electrolytic manganese dioxide rinse water and mill floor wash-down water manganese ion concentration can be lower for manganese ion concentration meeting height.But all bivalent ions waste water of manganese that contains all can be applicable to the present invention, not by the impact of Manganese in Waste Water ionic concn.Sulfur-containing waste water is the waste water containing barium sulphide and/or strontium sulfide.Barium strontium salt industry adopts reduction with carbon-leaching-process for carbonization production, and the compound of sulfide (barium sulphide and/or strontium sulfide) and other sulfur-bearing is contained in process recycled water and slag field in seeping water, such as polysulfide.Preferably in described sulfur-containing waste water adds, add sodium sulphite, to maintain S
2-concentration is at 2.5-3.0g/L.
Containing manganese sulfide and barium sulfate in solid-liquid separation gained filter cake, adopt sulfuric acid acidation, the manganese sulfide in filter cake is converted into solvable manganese salt, reaches the object reclaiming manganese.After above-mentioned sulfuric acid acidation filter cake, barium sulfate remains in acidifying residue, is further used for preparing barium sulphide.
The reaction equation of this step is:
MnSO
4+Ba(Sr)S→MnS↓+Ba(Sr)SO
4↓
(2) oxidation sweetening
Particle volume diameter is less than the Manganse Dioxide breeze of 120 microns (crossing 120 mesh sieves), the filtrate obtained with step (1) vulcanization reaction is pulled an oar, and obtains slurry, then loads in inclined tube;
Described slurry enters from the bottom of inclined tube, then from inclined tube top fluid, controls described flow rate of slurry at 0.2m/h-0.25m/h.Inclined tube inclination 40-50 degree, preferably 45 degree.Inclined tube is of a size of ￠ (700-1000) × (4000-8000) mm, preferred ￠ 800 × 6000mm.The low top, bottom of inclined tube is high, and therefore slurry liquid level exports liquid level higher than inclined tube, utilizes this potential difference to save the energy, has carried out preliminary solid-liquid separation, thus can improve the utilising efficiency of manganese oxide.Preferably, described inclined tube is thtee-stage shiplock.Described thtee-stage shiplock refers to, the upper liquid outlet of a upper inclined tube connects the bottoms material entrance of next inclined tube, and three inclined tubes are from beginning to end successively, forms series connection.Slurry enters from the bottom of the first inclined tube, then from the first inclined tube top fluid, then enters the second inclined tube, the 3rd inclined tube successively, control described slurry in each inclined tube flow velocity at 0.2m/h-0.25m/h.
The reaction equation of this step is:
S
2-+S
2- x+1+MnO
2→S+MnO
(3) solid-liquid separation
By the liquid solid-liquid separation obtained from inclined tube top, obtain manganese monoxide solid and reuse water.Gained reuse water is as middle water circulation use.Manganese monoxide solid is for the preparation of manganous sulfate.
Combination treatment of the present invention sulfur-containing waste water and Mn-bearing waste water, obtain the raw material of reproducible utilization, reduce processing cost.
Set forth the enforcement of method of the present invention below by specific embodiment, one skilled in the art will appreciate that this should not be understood to the restriction to the claims in the present invention scope.
Embodiment
Embodiment 1
(1) vulcanization reaction
In Mn-bearing waste water (electrolytic manganese dioxide rinse water, wherein manganous sulfate concentration is 3.41g/L), constantly adding sulfur-containing waste water, (barium sulphide waste water, wherein with S
2-meter concentration is at 2.5g/L), stirring at normal temperature is reacted, as [Mn in mixing solutions
2+] <1ppm time stop add sulfur-containing waste water and termination reaction, then solid-liquid separation, gained filtrate enter next step operation.
Solid-liquid separation gained filter cake adopts sulfuric acid acidation to reclaim manganese.Acidifying residue enters converter for the preparation of barium sulphide.
(2) oxidation sweetening
Commercial particle volume diameter is less than the Manganse Dioxide breeze of 120 microns (crossing 120 mesh sieves), the filtrate obtained with step (1) vulcanization reaction is pulled an oar, and obtains slurry, then loads in inclined tube.Inclined tube thtee-stage shiplock (three inclined tubes join end to end successively), every root inclined tube tilts 45 degree, is of a size of ￠ 800 × 6000mm.
Slurry enters from the bottom of the first inclined tube, then from the first inclined tube top fluid, then enters the second inclined tube, the 3rd inclined tube successively, control described slurry in each inclined tube flow velocity at 0.23m/h.
(3) solid-liquid separation
By the liquid solid-liquid separation obtained from the 3rd inclined tube top, obtain manganese monoxide solid and reuse water.Gained reuse water is as middle water circulation use.Manganese monoxide solid is for the preparation of manganous sulfate.
Embodiment 2
(1) vulcanization reaction
In Mn-bearing waste water (electrolytic manganese dioxide chemical combination wash heat pulp water, wherein manganous sulfate concentration is 41.20g/L), constantly adding sulfur-containing waste water, (barium sulphide waste water, wherein with S
2-meter concentration is at 3.0g/L), stirring at normal temperature is reacted, as [Mn in mixing solutions
2+] <1ppm time stop add sulfur-containing waste water and termination reaction, then solid-liquid separation, gained filtrate enter next step operation.
Solid-liquid separation gained filter cake adopts sulfuric acid acidation to reclaim manganese.Acidifying residue enters converter for the preparation of barium sulphide.
(2) oxidation sweetening
Commercial particle volume diameter is less than the Manganse Dioxide breeze of 120 microns (crossing 120 mesh sieves), the filtrate obtained with step (1) vulcanization reaction is pulled an oar, and obtains slurry, then loads in inclined tube.Inclined tube thtee-stage shiplock (three inclined tubes join end to end successively), every root inclined tube tilts 45 degree, is of a size of ￠ 800 × 6000mm.
Slurry enters from the bottom of the first inclined tube, then from the first inclined tube top fluid, then enters the second inclined tube, the 3rd inclined tube successively, control described slurry in each inclined tube flow velocity at 0.20m/h.
(3) solid-liquid separation
By the liquid solid-liquid separation obtained from the 3rd inclined tube top, obtain manganese monoxide solid and reuse water.Gained reuse water is as middle water circulation use.Manganese monoxide solid is for the preparation of manganous sulfate.
Embodiment 3
(1) vulcanization reaction
In Mn-bearing waste water (electrolytic manganese dioxide mill floor wash-down water, wherein manganous sulfate concentration is 2.04g/L), constantly adding sulfur-containing waste water, (barium sulphide waste water, wherein with S
2-meter concentration is at 2.7g/L), stirring at normal temperature is reacted, as [Mn in mixing solutions
2+] <1ppm time stop add sulfur-containing waste water and termination reaction, then solid-liquid separation, gained filtrate enter next step operation.
Solid-liquid separation gained filter cake adopts sulfuric acid acidation to reclaim manganese.Acidifying residue enters converter for the preparation of barium sulphide.
(2) oxidation sweetening
Commercial particle volume diameter is less than the Manganse Dioxide breeze of 120 microns (crossing 120 mesh sieves), the filtrate obtained with step (1) vulcanization reaction is pulled an oar, and obtains slurry, then loads in inclined tube.Inclined tube thtee-stage shiplock (three inclined tubes join end to end successively), every root inclined tube tilts 45 degree, is of a size of ￠ 800 × 6000mm.
Slurry enters from the bottom of the first inclined tube, then from the first inclined tube top fluid, then enters the second inclined tube, the 3rd inclined tube successively, control described slurry in each inclined tube flow velocity at 0.25m/h.
(3) solid-liquid separation
By the liquid solid-liquid separation obtained from the 3rd inclined tube top, obtain manganese monoxide solid and reuse water.Gained reuse water is as middle water circulation use.Manganese monoxide solid is for the preparation of manganous sulfate.
Gained reuse water, through routine analysis, the results are shown in Table 1.
Table 1
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Mn 2+ppm | 0.57 | 0.80 | 0.50 |
| S 2-ppm | 1.42 | 1.44 | 1.40 |
| pH | 7.6 | 7.6 | 7.0 |
The present invention adopts vulcanization reaction-oxidation desulfuration process, and combination treatment sulfur-containing waste water and Mn-bearing waste water, obtain the raw material of reproducible utilization, reduce processing cost.Mn in water in embodiment 1-3 gained
2+content between 0.57-0.50ppm, S
2-content is between 1.40-1.44ppm, and pH value, about 7, meets middle water circulation use standard, saved cost.
Claims (11)
1. a combination treatment method for sulfur-containing waste water and Mn-bearing waste water, the method comprises:
(1) vulcanization reaction
Sulfur-containing waste water is added, stirring reaction, as [Mn in mixing solutions in Mn-bearing waste water
2+] <1ppm time stopped reaction, then solid-liquid separation, gained filtrate enter next step operation;
(2) oxidation sweetening
Particle volume diameter is less than the Manganse Dioxide breeze of 120 microns, the filtrate making beating obtained with step (1) vulcanization reaction, obtains slurry, then loads in inclined tube;
Described slurry enters from the bottom of inclined tube, then from inclined tube top fluid, controls described flow rate of slurry at 0.2m/h-0.25m/h; And
(3) solid-liquid separation
By the liquid solid-liquid separation obtained from inclined tube top, obtain manganese monoxide solid and reuse water.
2. the combination treatment method of sulfur-containing waste water according to claim 1 and Mn-bearing waste water, is characterized in that, described Mn-bearing waste water is for containing the bivalent ions waste water of manganese.
3. the combination treatment method of sulfur-containing waste water according to claim 2 and Mn-bearing waste water, is characterized in that, described Mn-bearing waste water is the waste water of sulfur acid manganese.
4. the sulfur-containing waste water according to any one of claim 1-3 and the combination treatment method of Mn-bearing waste water, is characterized in that, described sulfur-containing waste water is the waste water containing barium sulphide and/or strontium sulfide.
5. the combination treatment method of sulfur-containing waste water according to claim 4 and Mn-bearing waste water, is characterized in that, in described sulfur-containing waste water adds, add sodium sulphite, to maintain S
2-concentration is at 2.5-3.0g/L.
6. the combination treatment method of sulfur-containing waste water and Mn-bearing waste water according to claim 1 or 5, is characterized in that, in step (1), described solid-liquid separation gained filter cake through sulfuric acid acidation, be separated after reclaim manganese.
7. the combination treatment method of sulfur-containing waste water according to claim 6 and Mn-bearing waste water, is characterized in that, gained filter cake is after acidifying, being separated, and acidifying residue enters converter as the raw material preparing barium sulphide.
8. the sulfur-containing waste water according to claim 1 or 7 and the combination treatment method of Mn-bearing waste water, is characterized in that, in step (2), and low top high dip 40-50 degree bottom described inclined tube.
9. the combination treatment method of sulfur-containing waste water according to claim 8 and Mn-bearing waste water, is characterized in that, in step (2), and low top high dip 45 degree bottom described inclined tube.
10. the combination treatment method of sulfur-containing waste water according to claim 8 and Mn-bearing waste water, is characterized in that, in step (2), described inclined tube is thtee-stage shiplock.
The combination treatment method of 11. sulfur-containing waste waters according to claim 1 or 10 and Mn-bearing waste water, it is characterized in that, in step (3), gained reuse water is as middle water circulation use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310648200.3A CN103613225B (en) | 2013-12-04 | 2013-12-04 | The combination treatment method of sulfur-containing waste water and Mn-bearing waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310648200.3A CN103613225B (en) | 2013-12-04 | 2013-12-04 | The combination treatment method of sulfur-containing waste water and Mn-bearing waste water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103613225A CN103613225A (en) | 2014-03-05 |
| CN103613225B true CN103613225B (en) | 2015-11-25 |
Family
ID=50163954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310648200.3A Expired - Fee Related CN103613225B (en) | 2013-12-04 | 2013-12-04 | The combination treatment method of sulfur-containing waste water and Mn-bearing waste water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103613225B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1425613A (en) * | 2003-01-28 | 2003-06-25 | 天津理工学院 | Process for united producing barium hydroxide and manganese sulfate |
| CN101704554A (en) * | 2009-07-16 | 2010-05-12 | 贵州红星发展股份有限公司 | Method for preparing manganese sulfate |
| CN102115187A (en) * | 2010-12-30 | 2011-07-06 | 何云 | Method for preparing manganese sulfide coproduced with strontium sulfate and ammonium sulfide by using manganese-containing waste liquor produced during production of hydroquinone |
-
2013
- 2013-12-04 CN CN201310648200.3A patent/CN103613225B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1425613A (en) * | 2003-01-28 | 2003-06-25 | 天津理工学院 | Process for united producing barium hydroxide and manganese sulfate |
| CN101704554A (en) * | 2009-07-16 | 2010-05-12 | 贵州红星发展股份有限公司 | Method for preparing manganese sulfate |
| CN102115187A (en) * | 2010-12-30 | 2011-07-06 | 何云 | Method for preparing manganese sulfide coproduced with strontium sulfate and ammonium sulfide by using manganese-containing waste liquor produced during production of hydroquinone |
Non-Patent Citations (1)
| Title |
|---|
| 用含硫废水治理含铜废水;王泾阳;《工业水处理》;19901231;第10卷(第4期);摘要和第1节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103613225A (en) | 2014-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101798119B (en) | Method for preparing manganese sulfate monohydrate | |
| CN110747329B (en) | Electrolytic manganese dioxide production method based on bagasse papermaking white mud | |
| CN105502441A (en) | Method for continuously producing cell-grade lithium carbonate | |
| CN101284204A (en) | Method for treating flue gas containing SO2 using red mud | |
| CN105226342A (en) | A kind of method utilizing the active material of waste lead acid battery to prepare new lead-acid battery | |
| CN104084041B (en) | A kind of zinc oxide desulfurization gives up the renovation process of agent | |
| CN104726702A (en) | Method for preparing manganese sulfate from high-sulfur manganese carbonate ores and manganese peroxide ores | |
| CN109045989A (en) | A kind of zinc oxide desulfurization new process | |
| CN103643256A (en) | Deep purification method for manganese sulfate solution in manganese metal production | |
| CN203173926U (en) | Wastewater treatment system applicable to organic amine method smoke desulfuration device | |
| CN101654308A (en) | Method for recycling valuable metals in acidic water by sodium sulfhydrate | |
| CN103880058B (en) | A kind of precipitated chalk production technique of falling magnesium increasing calcium | |
| CN108275707A (en) | The method of sodium oxide molybdena in efficient removal alumina producing Bayer process red mud | |
| CN107502740A (en) | One kind reclaims iron resource method from pyrolusite leached mud | |
| CN103074642A (en) | Process for recycling lead from waste lead-acid battery paste | |
| CN103613225B (en) | The combination treatment method of sulfur-containing waste water and Mn-bearing waste water | |
| CN104445337B (en) | A kind of ammonia alkali slops and bittern produce the method for low chlorine gypsum | |
| CN109264761A (en) | A kind of method that milk of lime process recycles calcium ions and magnesium ions in desulfurization wastewater | |
| CN103359700A (en) | Method for saving acid and reducing ammonium in ammonium phosphate production | |
| CN106865827A (en) | Sewage water treatment method and processing system | |
| CN110358936A (en) | A method of electrolytic manganese dioxide is prepared using pyrolusite | |
| CN104591291A (en) | Method for producing manganese sulfate by performing zinc electrodeposit anode slime treatment on sulfur dioxide flue gas | |
| CN109331620A (en) | A kind of calcium and magnesium composite desulfurizing agent and its calcium and magnesium compound desulfurizing process | |
| CN112499688B (en) | Recycling method of calcium and magnesium removing slag of manganese sulfate solution | |
| CN102492956B (en) | Electrolytic manganese dioxide and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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 |
Granted publication date: 20151125 Termination date: 20191204 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |