CN102285665B - Liquid phase chemical deposition modified natural zeolite and method for removing fluorine from water - Google Patents
Liquid phase chemical deposition modified natural zeolite and method for removing fluorine from water Download PDFInfo
- Publication number
- CN102285665B CN102285665B CN 201110151208 CN201110151208A CN102285665B CN 102285665 B CN102285665 B CN 102285665B CN 201110151208 CN201110151208 CN 201110151208 CN 201110151208 A CN201110151208 A CN 201110151208A CN 102285665 B CN102285665 B CN 102285665B
- Authority
- CN
- China
- Prior art keywords
- zeolite
- water
- modified
- solution
- natural zeolite
- 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
- Water Treatment By Sorption (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to liquid phase chemical deposition modified natural zeolite and a method for removing fluorine from water. In the invention, a sodium chloride(or zinc chloride)-aluminum sulfate(aluminum chloride or zirconium dichloride oxide) composite system is subjected to ion exchanger first, then natural zeolite is modified by means of liquid phase deposition to form a micelle structure, and finally the modified zeolite with high specific surface area, high porosity and high absorbability is obtained. The fluorine removal capacity of the modified zeolite reaches over 1,000mg/kg, and the modified zeolite has high fluorine removing effect particularly when used for fluorine-containing water at a lower concentration. The modified zeolite has a bright development and use prospect in the field of drinking water purification and fluorine removal and industrial water treatment.
Description
Technical field
The invention belongs to the environmentally conscious materials field, relate to a kind of liquid phase chemical deposition modified natural zeolite and reach the method that is used for removing fluor in water, thereby realize the removal purpose to fluorion in the water.
Background technology
Fluorine is one of trace element of needed by human, but intake too much can cause very large harm to HUMAN HEALTH, and according to China's sanitary standard of drinking water regulation, fluorine content must not surpass 1.0mg/L in the tap water.In China, water of high fluorine content is widely distributed, and according to statistics, China has 7,700 ten thousand people's tap water fluorine contents to exceed standard.At present, the method for defluorination mainly contains coagulation sedimentation, absorption method, electrocoagulation, electroosmose process, reverse osmosis method and ion exchange method both at home and abroad.Wherein widely used a kind of method is absorption method, and the fluorine adsorbent material of using mainly contains bone black, activated alumina, zeolite etc.Its mesolite has that cost is low, loading capacity is large, easy handling, the advantage such as renewable, therefore is most widely used in drinking water defluorination.
Natural zeolite has porousness and larger specific surface area, thereby has good ionic adsorption, switching performance, is widely used as sorbent material, is applied to drink water purifying and sewage disposal aspect, is good drinking water defluorination material.But natural zeolite has also adsorbed large quantity of moisture simultaneously owing to having a large amount of impurity in the duct, so that the adsorptive power of zeolite can not be brought into play, loading capacity is less.Therefore, generally come into one's own for the research work of natural zeolite modification in recent years.
Researcher in natural zeolite study on the modification process, with to skeleton structure of zeolite, surface tissue, ionic species as the modification starting point, and then microtexture, the ion-exchange performance of natural zeolite carried out modification, thereby realize the optimization to absorption property.Be used at present the natural zeolite modification acid treatment modification, alkali treatment modifying, ion exchange method modification, thermal treatment modification, microwave modification, surface modification and framework modification etc. have been arranged.Wherein using more is the ion exchange method modification.
Adopt Al in the traditional technology
3+, Zr
4+, Fe
3+Plasma carries out ion-exchanged to natural zeolite, foreign ion in the zeolite cavity is cemented out, thereby increase zeolite pores rate and specific surface area, obtain modified zeolite, although such method has certain effect to improving the zeolite adsorption performance, but because ion-exchange reagent can not fully be removed impurity in the duct, so that the zeolite adsorption performance can not be given full play to.Be used for the removing fluor in water capacity generally below 500mg/Kg with the zeolite of traditional method modification, can not well be applied in the production practice, therefore, need to traditional ion exchange process be improved.The liquid phase chemical deposition technology is to utilize between the liquid intermediate ion mutually that electrostatic interaction makes ion in the process of solid phase surface formation of deposits solid material, be mainly used at present thin-film material, powder body material and some composite manufactures, utilize the liquid phase chemical deposition principle by the nanoparticle deposition report that porous material carries out modification also not to be had.This patent combines ion exchange technique with the liquid phase chemical deposition technology, by ion exchange, remove impurity in the zeolite cavity, increases specific surface area and porosity; Act on the numerous surfaces of zeolite by liquid phase chemical deposition again and be formed with the micelle structure that is beneficial to absorption, thereby prepare the modified zeolite of high adsorption rate.The method is abundant modified natural zeolite, the effective ways that improve ion-exchange and absorption property.
In this patent, employing sodium-chlor (or zinc chloride)-Tai-Ace S 150 (or aluminum chloride, or chlorine oxygen zirconium) compound system, carry out first ion-exchange, by the mode of liquid deposition natural zeolite is carried out modification again.By control, under lower pH value, NaCl (or ZnCl
2) acidic solution can remove impurity in the zeolite cavity, carries out simultaneously the part ion exchange, with the natural zeolite activation for the elementary modified zeolite of ion-exchange easily occurs.Elementary modified zeolite after the activation is used Al again
2SO
4(or AlCl
3Or ZrOCl
2) solution soaking, and load Al (or Zr) central ion by deposition technique on each surface of zeolite, form the micelle structure, obtain finally that specific surface area is large, porosity is high, the modification defluorination zeolite that absorption property is good.
Summary of the invention
The object of the invention is to adopt the liquid phase chemical deposition technology that natural zeolite is carried out modification, to obtaining the defluorination material that specific surface area is large, porosity is high, absorption property is good.Invention is achieved through the following technical solutions.
A kind of liquid phase chemical deposition modified natural zeolite, step is as follows:
(1) preparation NaCl or ZnCl
2Activated solution: the NaCl that takes by weighing or ZnCl
2, join in the deionized water, be stirred to dissolving, being mixed with concentration is 0.2-1.0mol/L solution; Add the salt acid for adjusting pH to 2-3;
(2) pre-treatment natural zeolite: with tap water flushing 3-4 time, wash natural zeolite off surface impurity, put into baking oven and carry out drying, obtain clean natural zeolite;
(3) getting clean natural zeolite, is that the ratio of 1: 3 to 3: 4 (g/ml) joins NaCl or the ZnCl that step (1) is prepared according to the solid-liquid volume ratio
2Solution soaking 12-24h stirs in the immersion process frequently, and solid-liquid is fully contacted, to reach the purpose of abundant exchange;
(4) step (3) gained zeolite is fished for out, simply cleaned with clear water, put into baking oven after being filtered dry and carry out abundant drying, get final product to get elementary modified zeolite.
(5) preparation Al
2SO
4Or AlCl
3, or ZrOCl
2Central ion solution: the Al that takes by weighing
2(SO
4)
318H
2O or Al Cl
38H
2O or ZrOCl
28H
2O joins in the deionized water, is stirred to dissolving, and compound concentration is the solution of 0.2-1.0mol/L;
(6) with the elementary active zeolite of step (4) gained through Na or Zn modification, join Al
2(SO
4)
3Or Al Cl
3Or ZrOCl
2In the solution, the solid-liquid volume ratio is (g/ml) 1: 3 to 3: 4, soaks 12-24h, frequently stirs in the immersion process, and exchange is fully carried out;
(7) in the solidliquid mixture of upper step, splash into ammonia soln, make the pH of mixture transfer to 8-10, the liquid phase chemical deposition modification is carried out on each surface of zeolite;
(8) upper step gained zeolite is fished for out, simply cleaned with clear water, after being filtered dry the gained modified zeolite is put into baking oven and carry out abundant drying, can obtain final modified zeolite.
Adopt the modified natural zeolite of the present invention's preparation for the method for removing fluor in water, step is as follows:
(1) modified zeolite is placed the experiment volumetric flask, add fluoride ion water, the solid-liquid mass ratio is 1: 100 (g/ml); Soak more than 8 hours, frequently shake up therebetween and stir, to reach abundant absorption;
(2) get the fluorinated water that modified zeolite was processed, F-concentration in the fluorinated water after surely processing with fluoride ion electrode combination acidity instrumentation, and then calculate the defluorination capacity of modified zeolite; Reach more than the 1000mg/Kg.
The modified zeolite that adopts the technology of utilizing ion-exchange to combine with liquid phase chemical deposition of the present invention to prepare, porosity is high, specific surface area is large, and the defluorination capacity is high, can reach more than the 1000mg/Kg.Especially the less fluorinated water of concentration there is preferably defluorination effect, makes it at drink water purifying defluorination and Treatment of Industrial Water field wide development and application prospect be arranged.
Embodiment
Embodiment 1:
(1) takes by weighing 2.92g NaCl and place beaker, add deionized water and stirring to dissolving, change constant volume in the 250ml volumetric flask over to, get final product to get 0.2mol/L NaCl solution.Solution is changed in the reagent bottle, drip hydrochloric acid conditioning solution pH to 2.
(2) take by weighing ZrOCl
28H
2O 16.11g places beaker, adds deionized water and stirring to fully dissolving, changes constant volume in the 250ml volumetric flask over to, namely gets the ZrOCl of 0.2mol/L
2Solution changes in the reagent bottle.
(3) take by weighing the 50g natural zeolite, with tap water flushing 3 times, insert in the baking oven fully dry.
(4) gained zeolite in (3) is placed beaker, add 0.2mol/L NaCl solution 150ml, making solid-to-liquid ratio is 1: 3, soaks 12h.Frequently stir in the immersion process, solid-liquid is fully contacted, absorption is fully carried out.
(5) gained zeolite in (4) is fished for out, simply cleaned with clear water, after being filtered dry the gained modified zeolite is put into baking oven and carry out abundant drying, can obtain final modified zeolite.
(6) the elementary modified zeolite of gained in (5) is placed beaker, add the ZrOCl of 0.2mol/L
2Solution 150ml, making solid-to-liquid ratio is 1: 3, soaks 12h, frequently stirs in the immersion process, and exchange is fully carried out.
(7) in (6), splash into the ammonia soln of 1N in the gained solidliquid mixture, make the pH of mixture transfer to 8, the liquid phase chemical deposition modification is carried out on each surface of zeolite.
(8) gained zeolite in (7) is fished for out, simply cleaned with clear water, after being filtered dry the gained modified zeolite is put into baking oven and carry out abundant drying, can obtain final modified zeolite.
(9) take by weighing the 0.0547g Sodium Fluoride, place beaker, add deionized water, be mixed with and contain the water of high fluorine content solution that F-concentration is 20mg/L
(10) take by weighing gained modified zeolite 2g in (7), place test bottle, make water of high fluorine content 200ml in the adding (8) and carry out the defluorination experiment.Soak 8h, frequently shake up stirring therebetween.
(11) get the 500ml deionized water, the 57ml glacial acetic acid takes by weighing NaCl 58g, and Trisodium Citrate 12g is stirred to dissolving in the adding beaker, and dripping 6mol/L NaOH solution regulator solution pH is 5.5.Change constant volume in the 1L volumetric flask over to, produce buffered soln, change in the reagent bottle.
(12) get in fluorinated water 25ml that modified zeolite processed, (10) and make buffered soln 5ml, deionized water 20ml places beaker, stirs.Surely F-concentration in the fluorinated water after processing with PHS-25C type fluoride ion electrode combination acidity instrumentation, and then calculate the defluorination capacity of modified zeolite.
The defluorination capacity sees Table 1
Embodiment 2:
Step of preparation process is identical with embodiment 1, and difference is in described (1), takes by weighing 7.31g NaCl, is mixed with the solution that concentration is 0.5mol/L, regulates pH=2.5.In described (2), take by weighing ZrOCl
28H
2O 40.3g is mixed with the solution that concentration is 0.5mol/L.In described (3), with tap water flushing 4 times.In described (4), add 0.5mol/L NaCl solution 100ml, making solid-to-liquid ratio is 1: 2, soaks 18h.Add 0.5mol/L ZrOCl in described (6)
2Solution 100mL, solid-to-liquid ratio is 1: 2, soaks 18h.Add 1N ammoniacal liquor in described (7), with solidliquid mixture pH regulator to 8.
The defluorination capacity sees Table 1
Embodiment 3:
Step of preparation process is identical with embodiment 1, and difference is in described (1), takes by weighing 14.62g NaCl, is mixed with the solution that concentration is 1.0mol/L, regulates pH=3.In described (2), take by weighing ZrOCl
28H
2O 80.6g is mixed with the solution that concentration is 1.0mol/L.In described (4), add 1.0mol/L NaCl solution 67ml, making solid-to-liquid ratio is 3: 4, soaks 24h.Add 1.0mol/L ZrOCl in described (6)
2Solution 67mL, solid-to-liquid ratio is 3: 4, soaks 24h.Add 1N ammoniacal liquor in described (7), with solidliquid mixture pH regulator to 9.
The defluorination capacity sees Table 1
Embodiment 4
Preparation technology and flow process are identical with embodiment 1, and difference is in described (2), takes by weighing AlCl
38H
2O 27.14g is mixed with the solution that concentration is 0.4mol/L.In described (6), adding concentration is the AlCl of 0.4mol/L
3Solution soaking.
The defluorination capacity sees Table 1
Embodiment 5
Preparation technology and flow process are identical with embodiment 1, and difference is in described (2), takes by weighing Al
2(SO
4)
318H
2O 33.3g is mixed with the solution that concentration is 0.2mol/L.In described (6), adding concentration is the Al of 0.2mol/L
2(SO
4)
3Solution soaking.
The defluorination capacity sees Table 1
Embodiment 6
Preparation technology and flow process are identical with embodiment 1, and difference is in described (1), takes by weighing 17g ZnCl
2Be mixed with the solution that concentration is 0.5mol/L, regulate pH=2.In described (4), adding concentration is 0.5mol/L ZnCl
2Solution soaks.
The defluorination capacity sees Table 1
Embodiment 7
Preparation technology and flow process are identical with embodiment 6, and difference is in described (2), takes by weighing AlCl
38H
2O 27.14g is mixed with the solution that concentration is 0.4mol/L.In described (6), adding concentration is the AlCl of 0.4mol/L
3Solution soaking.
The defluorination capacity sees Table 1
Embodiment 8
Preparation technology and flow process are identical with embodiment 6, and difference is in described (2), takes by weighing Al
2(SO
4)
318H
2O 33.3g is mixed with the solution that concentration is 0.2mol/L.In described (6), adding concentration is the Al of 0.2mol/L
2(SO
4)
3Solution soaking.
The defluorination capacity sees Table 1
The example 1 that obtains is as shown in table 1 to the experimental result of example 8.
The defluorination capacity of modified zeolite in table 1 example
Annotate: defluorination capacity in the table 1
Q (mg/Kg) is saturated extent of adsorption,
C
0(mg/L) be the initial F-concentration of fluorine-containing water sample,
C
eF-concentration when (mg/L) being fluorine-containing water sample balance,
V (ml) is defluorination experiment fluorine-containing volume of water sample that time adds,
M (g) is added the modified zeolite quality when testing by defluorination.
All methods and technology of preparing that the present invention discloses and proposes, those skilled in the art can be by using for reference this paper content, the links such as appropriate change raw material and operational path realize, although method of the present invention and technology of preparing are described by preferred embodiment, person skilled obviously can change or reconfigure method as herein described and technological line within not break away from content of the present invention, spirit and scope, realizes final technology of preparing.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are deemed to be included in spirit of the present invention, scope and the content.
Claims (2)
1. liquid phase chemical deposition modified natural zeolite is characterized in that step is as follows:
(1) preparation NaCl or ZnCl
2Activated solution: the NaCl that takes by weighing or ZnCl
2, join in the deionized water, be stirred to dissolving, being mixed with concentration is 0.2-1.0mol/L solution; Add the salt acid for adjusting pH to 2-3;
(2) pre-treatment natural zeolite: with tap water flushing 3-4 time, wash natural zeolite off surface impurity, put into baking oven and carry out drying, obtain clean natural zeolite;
(3) get clean natural zeolite, being 1:3 according to the solid-liquid volume ratio joins NaCl or the ZnCl that step (1) is prepared to the ratio of 3:4g/ml
2Solution soaking 12-24h stirs in the immersion process frequently, and solid-liquid is fully contacted, to reach the purpose of abundant exchange;
(4) step (3) gained zeolite is fished for out, simply cleaned with clear water, put into baking oven after being filtered dry and carry out abundant drying, get final product to get elementary modified zeolite;
(5) preparation Al
2(SO
4)
3Or AlCl
3, or ZrOCl
2Central ion solution: the Al that takes by weighing
2(SO
4)
318H
2O or Al Cl
38H
2O or ZrOCl
28H
2O joins in the deionized water, is stirred to dissolving, and compound concentration is the solution of 0.2-1.0mol/L;
(6) with the elementary active zeolite of step (4) gained through Na or Zn modification, join Al
2(SO
4)
3Or Al Cl
3Or ZrOCl
2In the solution, the solid-liquid volume ratio be 1:3 to 3:4g/ml, soak 12-24h, frequently stir in the immersion process, exchange is fully carried out;
(7) in the solidliquid mixture of upper step, splash into ammonia soln, make the pH of mixture transfer to 8-10, the liquid phase chemical deposition modification is carried out on each surface of zeolite;
(8) upper step gained zeolite is fished for out, simply cleaned with clear water, after being filtered dry the gained modified zeolite is put into baking oven and carry out abundant drying, can obtain final modified zeolite.
2. the modified natural zeolite of claim 1 preparation is used for the method for removing fluor in water, it is characterized in that step is as follows:
(1) modified zeolite is placed the experiment volumetric flask, add fluoride ion water, the solid-liquid mass ratio is 1:100g/ml; Soak more than 8 hours, frequently shake up therebetween and stir, to reach abundant absorption;
(2) get the fluorinated water that modified zeolite was processed, fluorinion concentration in the fluorinated water after surely processing with fluoride ion electrode combination acidity instrumentation, and then calculate the defluorination capacity of modified zeolite; Reach more than the 1000mg/Kg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110151208 CN102285665B (en) | 2011-06-07 | 2011-06-07 | Liquid phase chemical deposition modified natural zeolite and method for removing fluorine from water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110151208 CN102285665B (en) | 2011-06-07 | 2011-06-07 | Liquid phase chemical deposition modified natural zeolite and method for removing fluorine from water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102285665A CN102285665A (en) | 2011-12-21 |
| CN102285665B true CN102285665B (en) | 2013-01-16 |
Family
ID=45332454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110151208 Expired - Fee Related CN102285665B (en) | 2011-06-07 | 2011-06-07 | Liquid phase chemical deposition modified natural zeolite and method for removing fluorine from water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102285665B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274561B (en) * | 2013-06-09 | 2014-03-05 | 谭振光 | Zeolite pyrolysis activation and temperature-control dynamic defluorination process technology of mineral water in medium-temperature hot spring |
| CN114751563B (en) * | 2022-06-14 | 2022-08-16 | 北京北方宏拓环境科技有限公司 | A step purifying filter for getting rid of acid mine in water sulphate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2210965A (en) * | 1937-07-03 | 1940-08-13 | Charles H Lewis | Purification of potable water |
| CN101088604A (en) * | 2007-06-14 | 2007-12-19 | 山东乾天工贸有限公司 | Process of preparing filter material for reducing fluoride content and improving water quality |
| CN101264440A (en) * | 2008-03-18 | 2008-09-17 | 上海大学 | Preparation of iron modified natural STI zeolite defluorination material and regeneration method |
| CN201567247U (en) * | 2009-09-17 | 2010-09-01 | 刘严蓬 | Natural zeolite purified water treatment device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1319857C (en) * | 2005-06-23 | 2007-06-06 | 复旦大学 | High silicon super stabilizing natural foresite and it preparation process |
-
2011
- 2011-06-07 CN CN 201110151208 patent/CN102285665B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2210965A (en) * | 1937-07-03 | 1940-08-13 | Charles H Lewis | Purification of potable water |
| CN101088604A (en) * | 2007-06-14 | 2007-12-19 | 山东乾天工贸有限公司 | Process of preparing filter material for reducing fluoride content and improving water quality |
| CN101264440A (en) * | 2008-03-18 | 2008-09-17 | 上海大学 | Preparation of iron modified natural STI zeolite defluorination material and regeneration method |
| CN201567247U (en) * | 2009-09-17 | 2010-09-01 | 刘严蓬 | Natural zeolite purified water treatment device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102285665A (en) | 2011-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106750356A (en) | A kind of method that metal-organic framework materials of utilization UiO 66 purify selenium-containing wastewater | |
| CN105126742B (en) | A kind of method using modified kaolin sorbent treatment fluoride waste | |
| CN101716489A (en) | Denitrification dephosphorization antibacterial composite water treatment material used for water reclamation | |
| CN104525090A (en) | Absorbent used in sewage phosphorus removal, and preparation method thereof | |
| CN104014314B (en) | Bio-adsorbent, preparation method and application | |
| CN101920190B (en) | Zeolite modifying method and application thereof in removing arsenic in water | |
| CN102527328A (en) | Method for preparing adsorbing material for removing phosphate from sewage | |
| CN104148008B (en) | High-efficiency adsorbent of a kind of heavy metal ion and preparation method thereof and application | |
| CN104001471A (en) | Preparation method of silicon dioxide immobilized hydroxyapatite material | |
| CN110280209A (en) | A kind of water systems'phosphorus adsorbent material and its preparation, application method | |
| CN108970587A (en) | A kind of chitosan crosslinked adsorbent of composite modified montmorillonite and preparation method thereof | |
| CN110102265A (en) | For the load zirconium biology compound adsorbent and regeneration method of removing fluor in water and application | |
| CN102285665B (en) | Liquid phase chemical deposition modified natural zeolite and method for removing fluorine from water | |
| CN103071452B (en) | Method for preparing lanthanum or cerium pillared montmorillonite fluorine removal agent | |
| CN102335585B (en) | Method for preparing zirconium-modified attapulgite clay adsorbent and method for removing fluorine from water by using adsorbent | |
| CN107376829A (en) | A kind of preparation method for carrying iron powder coal ash arsenic-removing adsorption agent | |
| CN102872812A (en) | Composite adsorbing material for removing fluorine ions in water and preparation method thereof | |
| CN102976431B (en) | Drinking water purifying agent and preparation method thereof | |
| CN101215035B (en) | Method for removing fluorine ion from water by using zirconium oxide carried molecular screen | |
| KR101292524B1 (en) | Preparation Method of complex comprising a porous alginic acid gel | |
| CN101088604A (en) | Process of preparing filter material for reducing fluoride content and improving water quality | |
| CN109095546B (en) | Method for preparing hydrogen by cooperation of photocatalytic treatment of wastewater | |
| CN106379955A (en) | Waste water treating agent and application thereof | |
| CN102107907B (en) | Porous nano hydrated titanium dioxide dearsenifying material and preparation method thereof | |
| CN203890090U (en) | Simple suspended phosphorous removal device for in-situ purification of polluted surface water body |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130116 Termination date: 20130607 |