CN102671649A - Preparation method of nano photochemical catalytic oxidizer for removing arsenic (III) in drinking water - Google Patents

Preparation method of nano photochemical catalytic oxidizer for removing arsenic (III) in drinking water Download PDF

Info

Publication number
CN102671649A
CN102671649A CN2012100973543A CN201210097354A CN102671649A CN 102671649 A CN102671649 A CN 102671649A CN 2012100973543 A CN2012100973543 A CN 2012100973543A CN 201210097354 A CN201210097354 A CN 201210097354A CN 102671649 A CN102671649 A CN 102671649A
Authority
CN
China
Prior art keywords
preparation
arsenic
alcohol
nano
drinking water
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.)
Pending
Application number
CN2012100973543A
Other languages
Chinese (zh)
Inventor
姚淑华
张亚星
石中亮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenyang University of Chemical Technology
Original Assignee
Shenyang University of Chemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenyang University of Chemical Technology filed Critical Shenyang University of Chemical Technology
Priority to CN2012100973543A priority Critical patent/CN102671649A/en
Publication of CN102671649A publication Critical patent/CN102671649A/en
Pending legal-status Critical Current

Links

Images

Abstract

The invention discloses a preparation method of nano photochemical catalytic oxidizer for removing arsenic (III) in drinking water, and relates to a preparation method of oxidizer. The method comprises the following steps: selecting activated carbon fiber material with the pore volume being 0.100 to 0.500cm3/g, preparing titanium dioxide sol, dissolving 20mL of titanium salt in 40ml of absolute alcohol solution, adding 8 to 12mL of acetylacetone and 12 to 20mL of glacial acetic acid and performing magnetic stirring, then adding 80 to 100mL of absolute alcohol solution and 15 to 20mL of water mixed liquor, preparing activated carbon fiber carrying titanium dioxide, weighing 10 to 20g of pretreated activated carbon fiber to be added into 100 to 200mL of titanium dioxide sol, after dipping the pretreated activated carbon fiber for 12 to 48h, evaporating solvent to be dry, and calcining for 1 to 2h to obtain the nano photochemical catalytic oxidizer for removing arsenic (III). The oxidizer has high oxidation capacity and a small volume, is safe and stable, and is easy to store and transport.

Description

The preparation method of a kind of Removal of Arsenic in Drinking Water (III) nano-photo catalytic oxidant
Technical field
The present invention relates to the preparation method of the photochemical catalytic oxidation agent of As in the water body (III), specifically to the preparation method of a kind of loaded nano photochemical catalytic oxidation agent of As (III) oxidation removal.
Background technology
Arsenic is carcinogenic, the mutagenesis factor, and animal is also had teratogenesis, and long-term arsenic exposes and can cause black leg, neuralgia, injury of blood vessel, the morbidity of increase heart disease and cause organ cancerations such as skin, lung, liver, bladder and prostate etc.Human body mainly is through food and drinking water to the absorption approach of arsenic, and wherein digestive system is most important approach to the absorption of arsenic., the arsenic removal of therefore drinking water is the effective measures of control endemic arsenic poisoning.The World Health Organization revised the maximum permissible concentration of drinking water arsenic in 1993 again, confirmed as 10 μ gL -1The European Union and the U.S. have reformulated drinking water arsenic content standard, and the maximum permissible concentration of drinking water arsenic is from 50 μ gL -1Drop to 10 μ gL -1New sanitary standard has proposed requirements at the higher level to the removal and the technology of arsenic.
Arsenic in the drinking water mainly comprises pentavalent arsenic As (V) and trivalent arsenic As (III), and wherein As (III) has stronger toxicity.The content of As in the underground water of certain areas (III) is higher relatively, can reach more than 70%.In numerous arsenic removal technologies, absorption method is widely used in the purification arsenic removal of drinking-water owing to characteristics such as efficient are high, the processing flow is big, easy and simple to handle, cost is low.Yet existing adsorbent is generally better to the adsorptivity of As (V), and relatively poor to the absorption property of As (III), therefore the removal to As (III) is a difficult point of Removal of Arsenic in Drinking Water.Some technologies are As (V) through adding oxidant with the As in the drinking water (III) pre-oxidation; Remove to reach the purpose of effective removal arsenic with adsorbent again; Oxidant commonly used has potassium permanganate, synthetic glauconite, clorox, ozone, chlorine, hydrogen peroxide, ferrate etc., yet all there is certain limitation in these methods.For adapting to the safety standard of arsenic in the new drinking-water, need to seek more effective As (III) method for oxidation.Some nearest researchs show nano-TiO 2Photochemical catalyst can be As (V) with As (III) the efficient oxidation.Though nano-TiO 2Have advantages such as specific surface is big, reactivity is good, but have shortcomings such as the penetration depth that is prone to cohesion, handles rear catalyst difficult separation and recycling and light is low, make this method be difficult to practicability.Exploitation support type catalysis material can overcome above-mentioned shortcoming, promptly As (III) is had the metal oxide supported in porous material of better photocatalytic oxidation properties.About loaded nano TiO 2Photocatalysis degradation organic contaminant has more research, but activated carbon fiber loaded nano-TiO 2In drinking water As (III) oxidation field, be not widely used as yet.
Summary of the invention
The object of the present invention is to provide a kind of Removal of Arsenic in Drinking Water (
Figure 2012100973543100002DEST_PATH_IMAGE001
) preparation method of nano-photo catalytic oxidant, utilize nano-TiO 2Have characteristics such as specific area is big, active height, nano-TiO 2Load to the surperficial and inner of NACF, it is cheap relatively to develop cost, the environmental protection oxidant that oxidation susceptibility is high.Oxidant only contains carbon, titanium, three kinds of common elements of oxygen, and health is not had risk.
Technical scheme of the present invention is:
The preparation method of a kind of Removal of Arsenic in Drinking Water (
Figure 731933DEST_PATH_IMAGE001
) nano-photo catalytic oxidant, operation as follows:
Figure 345579DEST_PATH_IMAGE002
Choosing pore volume is 0.100-0.500 cm 3The commercially available NACF of/g boils 3-5 h, sonicated 60-120 min, 100-120 ℃ of vacuum drying 24 h earlier in deionized water;
Figure 2012100973543100002DEST_PATH_IMAGE003
adds absolute alcohol in titanium salt, titanium salt and absolute alcohol volume ratio are 1:2;
Splash into stabilizing agent acetylacetone,2,4-pentanedione and sustained release agent glacial acetic acid under
Figure 694521DEST_PATH_IMAGE004
magnetic agitation, the volume ratio of stabilizing agent, sustained release agent and titanium salt is about 2:3:4;
Figure 2012100973543100002DEST_PATH_IMAGE005
drips the mixed liquor of anhydrous alcohol and water by titanium salt, absolute alcohol, water volume ratio 1:4:1; After dropwising, sonic oscillation 1～3 h leaves standstill 24～72 h;
Under room temperature; The pretreated activated carbon fiber of 10～20 g is put into 100～200 mL TiO 2 sols that prepared flood 12～48 h; Solvent evaporated is calcined 1～2 h and is got product in Muffle furnace under the nitrogen protection.
The preparation method of described a kind of Removal of Arsenic in Drinking Water (
Figure 604150DEST_PATH_IMAGE001
) nano-photo catalytic oxidant, its said titanium salt is titanyl sulfate, butyl titanate, titanium tetrachloride.
The preparation method of described a kind of Removal of Arsenic in Drinking Water (
Figure 203628DEST_PATH_IMAGE001
) nano-photo catalytic oxidant, the low-carbon (LC) 2-4 unit alcohol that its said alcoholic solution is C1-C6 monohydric alcohol, C2-C8.
The preparation method of described a kind of Removal of Arsenic in Drinking Water (
Figure 169310DEST_PATH_IMAGE001
) nano-photo catalytic oxidant, its said monohydric alcohol is ethanol or propyl alcohol; Low-carbon (LC) 2-4 unit alcohol is ethylene glycol or glycerine.
The present invention has following advantage:
1. oxidation rate is fast, and oxidant of the present invention (2.0 g/L) can be with 4 mgL in 60 min -1All oxidations of As (III).
2. the preparation method is simple, and is with low cost.
Figure 39308DEST_PATH_IMAGE002
reaction condition is gentle: reaction at normal temperatures and pressures; Common laboratory, medium-sized and small enterprises can prepare, and can not burn, dangerous situation such as blast.
Figure 166664DEST_PATH_IMAGE003
oxidant itself is safe, economical, does not contain the harm element.This oxidant main component is titanium (and oxide), charcoal, and health is safe from harm.Get into public drinking water source system even leaking appears in something unexpected happened (like Act for God factor such as earthquake, tsunami, cyclone), oxidant, also can not pollute the water source.
3. cost of investment is low, is prone to transform go into operation.This oxidant production equipment needed thereby is simple, invests for a short time, and general medium-sized and small enterprises can be realized producing in batches.And usually economy is backward relatively in high arsenic area, and this point has realistic meaning and economic implications especially.
3. oxidant application life of the present invention is long, is easy to regeneration.Compare with other commercially available oxidant, this oxidant is long service life not only, and regeneration easily, and regeneration rear oxidation ability can improve the economic performance of this oxidant greatly up to more than 91.7% of former oxidability.
4 oxidants store, convenient transportation.Oxidant volume of the present invention is little, and safety and stability is easy to store, transport.
Description of drawings
Fig. 1 is the impact analysis figure of nano-photo catalytic oxidant consumption to As ( ) oxygenation efficiency;
Fig. 2 recycles the impact analysis figure of number of times to As (
Figure 757231DEST_PATH_IMAGE001
) oxygenation efficiency for the nano-photo catalytic oxidant.
The specific embodiment
The present invention is through test of many times, and As (
Figure 747315DEST_PATH_IMAGE001
) oxidation effectiveness is better.Below in conjunction with accompanying drawing the present invention is done further concrete description, but enforcement of the present invention is not limited to this.
Embodiment 1
The selection of material is: the selecting hole volume is 0.503 cm 3The activated carbon fiber of/g, single alcohol (C 1-C 6), the many alcohol series of low-carbon (LC) (C 1-C 10), acetylacetone,2,4-pentanedione, glacial acetic acid, deionized water, inert gas (common) etc.
Concrete steps are:
(1) choosing commercially available pore volume is 0.503 cm 3The active-carbon fibre material of/g boils 3 h in the boiling water (deionized water), sonicated 60 min;
(2) at room temperature; In the there-necked flask of 250 mL that magnetic stirring apparatus, NACF, dropping funel are housed; Add 20 mL butyl titanates and be dissolved in 40 mL absolute ethyl alcohols; Be added dropwise to 10 mL acetylacetone,2,4-pentanediones and 15 mL glacial acetic acid under the magnetic agitation, add the mixed liquor of 80 mL anhydrous alcohol solutions and 15 mL water again.
(3) dropwise back sonic oscillation 2 h, leave standstill 48 h.
(4) take by weighing pretreated activated carbon fiber 15 g, put into the 150 mL TiO that prepared 2After flooding 48 h in the colloidal sol, 80 ℃ of solvent evaporated, dry 12 h.
(5) under nitrogen protection, calcine 2 h in the Muffle furnace, temperature is 500 ℃.
(6) As ( ) initial concentration is 4 mg/L; The pH value is to add 0.5 respectively under 8 conditions; 1.0 1.5 g/L nano-photo catalytic oxidants carry out As (
Figure 619642DEST_PATH_IMAGE001
) oxidation test.
Can find out from accompanying drawing 1: nano-photo catalytic oxidant consumption has remarkable difference to the effect of As (
Figure 927127DEST_PATH_IMAGE001
) oxidation; Increase along with photochemical catalytic oxidation agent consumption; As (
Figure 506138DEST_PATH_IMAGE001
) oxygenation efficiency raises; When photochemical catalytic oxidation agent consumption was 1.5 g/L, 4 mg/L arsenic (
Figure 303192DEST_PATH_IMAGE001
) can be by complete oxidation in 60min.
Embodiment 2
The selection of material is: the selecting hole volume is 0.503 cm 3The activated carbon fiber of/g, single alcohol (C 1-C 6), the many alcohol series of low-carbon (LC) (C 1-C 10), acetylacetone,2,4-pentanedione, glacial acetic acid, deionized water, inert gas (common) etc.
Concrete steps are:
(1) choosing commercially available pore volume is 0.503 cm 3The active-carbon fibre material of/g boils 3 h in the boiling water (deionized water), sonicated 60 min;
(2) at room temperature; In the there-necked flask of 250 mL that magnetic stirring apparatus, NACF, dropping funel are housed; Add 20 mL butyl titanates and be dissolved in 40 mL absolute ethyl alcohols; Be added dropwise to 10 mL acetylacetone,2,4-pentanediones and 15 mL glacial acetic acid under the magnetic agitation, add the mixed liquor of 80 mL anhydrous alcohol solutions and 15 mL water again.
(3) dropwise back sonic oscillation 2 h, leave standstill 48 h.
(4) take by weighing pretreated activated carbon fiber 15 g, put into the 150 mL TiO that prepared 2After flooding 48 h in the colloidal sol, 80 ℃ of solvent evaporated, dry 12 h.
(5) under nitrogen protection, calcine 2 h in the Muffle furnace, temperature is 500 ℃.
(6) As (
Figure 849711DEST_PATH_IMAGE001
) initial concentration is 4 mg/L; Photochemical catalytic oxidation agent consumption is 1.5 g/L, and the pH value is cyclic oxidation As ( ) test of carrying out the photochemical catalytic oxidation agent under 8 conditions.
Can find out from accompanying drawing 2: this nano-photo catalytic oxidant is recycling (
Figure 158519DEST_PATH_IMAGE001
) oxidability that still has higher As after four times, and the oxygenation efficiency of As in 120 min (
Figure 814891DEST_PATH_IMAGE001
) is still more than 88%.So the nano-photo catalytic oxidant of this development test has application promise in clinical practice.

Claims (4)

1. the preparation method of a Removal of Arsenic in Drinking Water (
Figure 2012100973543100001DEST_PATH_IMAGE001
) nano-photo catalytic oxidant is characterized in that: operation as follows:
Figure 636940DEST_PATH_IMAGE002
Choosing pore volume is 0.100-0.500 cm 3The commercially available NACF of/g boils 3-5 h, sonicated 60-120 min, 100-120 ℃ of vacuum drying 24 h earlier in deionized water;
Figure 2012100973543100001DEST_PATH_IMAGE003
adds absolute alcohol in titanium salt, titanium salt and absolute alcohol volume ratio are 1:2;
Splash into stabilizing agent acetylacetone,2,4-pentanedione and sustained release agent glacial acetic acid under
Figure 207860DEST_PATH_IMAGE004
magnetic agitation, the volume ratio of stabilizing agent, sustained release agent and titanium salt is about 2:3:4;
Figure 2012100973543100001DEST_PATH_IMAGE005
drips the mixed liquor of anhydrous alcohol and water by titanium salt, absolute alcohol, water volume ratio 1:4:1; After dropwising, sonic oscillation 1～3 h leaves standstill 24～72 h;
Under room temperature; The pretreated activated carbon fiber of 10～20 g is put into 100～200 mL TiO 2 sols that prepared flood 12～48 h; Solvent evaporated is calcined 1～2 h and is got product in Muffle furnace under the nitrogen protection.
2. the preparation method of a kind of Removal of Arsenic in Drinking Water according to claim 1 (
Figure 191308DEST_PATH_IMAGE001
) nano-photo catalytic oxidant, it is characterized in that: said titanium salt is titanyl sulfate, butyl titanate, titanium tetrachloride.
3. the preparation method of a kind of Removal of Arsenic in Drinking Water according to claim 1 (
Figure 691560DEST_PATH_IMAGE001
) nano-photo catalytic oxidant is characterized in that: said alcoholic solution is the low-carbon (LC) 2-4 unit alcohol of C1-C6 monohydric alcohol, C2-C8.
4. the preparation method of a kind of Removal of Arsenic in Drinking Water according to claim 1 (
Figure 174494DEST_PATH_IMAGE001
) nano-photo catalytic oxidant, it is characterized in that: said monohydric alcohol is ethanol or propyl alcohol; Low-carbon (LC) 2-4 unit alcohol is ethylene glycol or glycerine.
CN2012100973543A 2012-04-05 2012-04-05 Preparation method of nano photochemical catalytic oxidizer for removing arsenic (III) in drinking water Pending CN102671649A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2012100973543A CN102671649A (en) 2012-04-05 2012-04-05 Preparation method of nano photochemical catalytic oxidizer for removing arsenic (III) in drinking water

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2012100973543A CN102671649A (en) 2012-04-05 2012-04-05 Preparation method of nano photochemical catalytic oxidizer for removing arsenic (III) in drinking water

Publications (1)

Publication Number Publication Date
CN102671649A true CN102671649A (en) 2012-09-19

Family

ID=46804589

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2012100973543A Pending CN102671649A (en) 2012-04-05 2012-04-05 Preparation method of nano photochemical catalytic oxidizer for removing arsenic (III) in drinking water

Country Status (1)

Country Link
CN (1) CN102671649A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102910767A (en) * 2012-10-17 2013-02-06 广东工业大学 Method for removing arsenic by loading titanium dioxide with activated carbon fiber hydrothermal method by means of photoelectrocatalysis oxidation
CN103691417A (en) * 2013-12-24 2014-04-02 南京大学 Preparation method of TiO2/ACF (Active Carbon Fiber) catalytic material and application thereof
CN103752268A (en) * 2014-01-16 2014-04-30 广东工业大学 Preparation method of filter core for adsorbing heavy metal, arsenic and fluorine in drinking water and application thereof
CN105129959A (en) * 2015-07-24 2015-12-09 南京大学 Method of photo-oxidizing treatment on trivalent arsenic in water through small-molecular diketone
CN105561969A (en) * 2016-03-02 2016-05-11 福建农林大学 Preparation and application of porous TixSn1-xO2 solid solution microspheres
CN103691417B (en) * 2013-12-24 2016-11-30 南京大学 A kind of TiO2the preparation method of/ACF catalysis material and application
CN106238059A (en) * 2016-07-13 2016-12-21 中国科学院化学研究所 A kind of remove the composite photo-catalyst of arsenic from underwater, preparation method, method for purifying water and system

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1702202A (en) * 2005-06-22 2005-11-30 中山大学 Active carbon fiber containing nano titanium dioxide particles and its preparation method and uses
CN101318129A (en) * 2008-07-23 2008-12-10 刘守新 Supported optical catalyst and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1702202A (en) * 2005-06-22 2005-11-30 中山大学 Active carbon fiber containing nano titanium dioxide particles and its preparation method and uses
CN101318129A (en) * 2008-07-23 2008-12-10 刘守新 Supported optical catalyst and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHUHUA YAO ET AL.: "Photocatalytic Oxidation of Arsenite by a Composite of Titanium Dioxide and Activated Carbon Fiber", 《PHOTOCHEMISTRY AND PHOTOBIOLOGY》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102910767A (en) * 2012-10-17 2013-02-06 广东工业大学 Method for removing arsenic by loading titanium dioxide with activated carbon fiber hydrothermal method by means of photoelectrocatalysis oxidation
CN102910767B (en) * 2012-10-17 2014-04-02 广东工业大学 Method for removing arsenic by loading titanium dioxide with activated carbon fiber hydrothermal method by means of photoelectrocatalysis oxidation
CN103691417A (en) * 2013-12-24 2014-04-02 南京大学 Preparation method of TiO2/ACF (Active Carbon Fiber) catalytic material and application thereof
CN103691417B (en) * 2013-12-24 2016-11-30 南京大学 A kind of TiO2the preparation method of/ACF catalysis material and application
CN103752268A (en) * 2014-01-16 2014-04-30 广东工业大学 Preparation method of filter core for adsorbing heavy metal, arsenic and fluorine in drinking water and application thereof
CN103752268B (en) * 2014-01-16 2015-11-18 广东工业大学 The filter core preparation method and application of heavy metal and arsenic, fluorine in absorption drinking water
CN105129959A (en) * 2015-07-24 2015-12-09 南京大学 Method of photo-oxidizing treatment on trivalent arsenic in water through small-molecular diketone
CN105129959B (en) * 2015-07-24 2017-06-16 南京大学 Using the method for trivalent arsenic in small molecule diketone photooxidation treatment water
CN105561969A (en) * 2016-03-02 2016-05-11 福建农林大学 Preparation and application of porous TixSn1-xO2 solid solution microspheres
CN106238059A (en) * 2016-07-13 2016-12-21 中国科学院化学研究所 A kind of remove the composite photo-catalyst of arsenic from underwater, preparation method, method for purifying water and system

Similar Documents

Publication Publication Date Title
Yang et al. Oxygen and chlorine dual vacancies enable photocatalytic O2 dissociation into monatomic reactive oxygen on BiOCl for refractory aromatic pollutant removal
CN102671649A (en) Preparation method of nano photochemical catalytic oxidizer for removing arsenic (III) in drinking water
Huang et al. Photosensitized peroxidase mimicry at the hierarchical 0D/2D heterojunction‐like quasi metal‐organic framework interface for boosting biocatalytic disinfection
CN103551168B (en) A kind ofly be applied to fixed bed catalyst without mercury preparing vinyl chloride and preparation method thereof
CN101485987B (en) Catalyst for normal temperature and pressure catalysis wet-type oxidation technology and preparation method
Abdelhamid Solid acid zirconium oxo sulfate/carbon-derived UiO-66 for hydrogen production
CN109876848B (en) Limited CoCNx @ C composite catalyst and preparation method and application thereof
CN103586048B (en) A kind of nano Pd particle magnetic catalyst, preparation and react for liquid-phase catalysis
CN102451711A (en) Industrial wastewater treatment catalyst and preparation method thereof
CN105170178B (en) A kind of catalyst for preparing propylene with propane dehydrogenation and preparation method thereof
CN103285887A (en) Kieselguhr loading solid superacid type Fenton catalyst preparation method
CN111188196B (en) Preparation and application of graphene composite fiber non-woven fabric for catalytic degradation of neurogenic chemical warfare agent
CN103157471A (en) Deoxidation catalyst for olefin gas, preparation method and application thereof
Zhang et al. Ce-doped MIL-125-NH2 coupled Ce4+/Ce3+ and Ti4+/Ti3+ redox mediators for thermo-enhanced photocatalytic oxidative desulfurization
CN102211026A (en) Composite catalytic material capable of synchronously capturing and recycling carbon dioxide and preparation method thereof
CN105289587A (en) Supported-type precious metal photocatalyser and preparation method thereof
CN104492433A (en) Adsorption catalyst based on activated carbon felt base as well as preparation method and application of adsorption catalyst
CN104478647B (en) A kind of aqueous catalysis biomass-making is for the method for hexane
Wang et al. Life time enhanced Fenton-like catalyst by dispersing iron oxides in activated carbon: Preparation and reactivation through carbothermal reaction
Li et al. Heteropolyacids supported on micro/mesoporous materials PMoW@ HKUST-1@ ZSM-5-MCM-41: Effective catalyst for oxidative desulfurization with oxygen
CN107185592A (en) A kind of preparation method of photocatalysis performance mixed nanometer Metal-organic frame
CN104399460A (en) Catalyst for industrial wastewater treatment and preparation method of catalyst
Mondol et al. Zirconium oxide@ N-doped porous carbons with oxygen vacancies, derived from zirconium chloride embedded metal-azolate framework-6: A new oxidative desulfurization catalyst
CN102218317A (en) Preparation method of catalyst for effectively catalyzing and oxidating medical contaminations in water
Ma et al. Photocatalytic oxidation degradation of tetracycline over La/Co@ TiO2 nanospheres under visible light

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20120919