CN102698581A - Method for producing sodium sulfate and sodium nitrate by simultaneous desulfurization and denitrification by soda-citric acid cobalt (II) - Google Patents

Method for producing sodium sulfate and sodium nitrate by simultaneous desulfurization and denitrification by soda-citric acid cobalt (II) Download PDF

Info

Publication number
CN102698581A
CN102698581A CN2012101678592A CN201210167859A CN102698581A CN 102698581 A CN102698581 A CN 102698581A CN 2012101678592 A CN2012101678592 A CN 2012101678592A CN 201210167859 A CN201210167859 A CN 201210167859A CN 102698581 A CN102698581 A CN 102698581A
Authority
CN
China
Prior art keywords
denitration
citric acid
soda
cobalt
flue gas
Prior art date
Application number
CN2012101678592A
Other languages
Chinese (zh)
Inventor
刘盛余
能子礼超
曲兵
邱伟
Original Assignee
成都信息工程学院
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 成都信息工程学院 filed Critical 成都信息工程学院
Priority to CN2012101678592A priority Critical patent/CN102698581A/en
Publication of CN102698581A publication Critical patent/CN102698581A/en

Links

Classifications

    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention discloses a technology for producing sodium sulfate and sodium nitrate by simultaneous wet flue gas desulfurization and denitrification by soda-citric acid cobalt (II). By the technology, SO2 and NO can be converted into Na2SO4 and NaNO3 respectively, so as to realize reclamation of SO2 and NO. The method is different from the general way of converting NO into N2 by denitration, adopts the conventional absorption process, has a mild operation condition, is performed at a normal temperature and pressure, has high desulfurization and denitrification ratio, is small in investment, and low in operation cost, and the absorption liquid is easy to regenerate.

Description

Soda-citric acid closes the method that cobalt (II) while desulphurization denitration is produced sodium sulphate and sodium nitrate
Technical field
The present invention relates to smoke gas treatment and control technology field, specifically is exactly flue gas and desulfurizing and denitrifying (SO 2And NOx), especially adopt soda and citric acid to close the technology that cobalt (II) wet flue gas while desulphurization denitration is produced sodium sulphate and sodium nitrate.
Background technology
China primary energy constitute and consumption in, the shared ratio of coal is up to 70%, wherein the coal-burning power plant is again China's consumption coal and sulfur dioxide (SO 2) and the rich and influential family of nitrogen oxide (NOx) discharging.SO 2Reaching NOx is the major pollutants of atmosphere, and they can produce acid rain, form photochemical fog, destroy ozone, bring great harm for environment and human health.According to statistics, 2006, China SO 2Discharge capacity surpassed 2,500 ten thousand t, be SO in the world 2The-discharging big country; Meanwhile, the discharge capacity of NOx has also surpassed 1,000 ten thousand t, and China is caused by acid rain pollution year, direct economic loss was above 1,100 hundred million yuan.Therefore control the SO of coal-burning power plant's discharging 2And NOx, be present China Air Pollution Control field one of urgent task the most.If to SO 2Reach NOx and administer respectively, not only floor space is big, and investment and operating cost height.For adapting at present and the needs of following Air Pollution Control, exploitation is the flue gas desulfurization and denitrification new technology simultaneously, and new equipment becomes the development trend in this field gradually.
At present, the flue gas and desulfurizing and denitrifying technical method by absorbent with remove different wet method and the dry method of being divided into of product state.Dry method is to treatment S O 2The flue gas of/NOx<1 is more suitable, and wet method is fit to treatment S O 2The flue gas that content is higher.General SO in the flue gas 2Concentration is about 2000ppm; NOx is 500ppm (mainly being NO), so the wet process of FGD denitration is more effective and comparatively economical than dry method, wherein wet fuel gas desulfurizing technology is used the widest in thermal power plant in addition; Desulfuration efficiency is high, so wet method while desulphurization denitration technology has very big development potentiality.Wet process of FGD denitration key is denitration.95% of NOx is NO in the flue gas, and NO is insoluble in water, and therefore conventional alkali absorption method is invalid to NO.Simultaneously since the NO concentration in the flue gas between 0.02-0.1% (V), the reaction speed of autoxidation is very low.
Through years of researches, developed various method of denitration both at home and abroad, like catalytic reduction method, catalytic decomposition method, absorption process; Absorption method, the electron ray irradiation, the oxidation absorption process, liquid phase reductions etc. (are seen Nature, 1990; 343:151-153, Nature, 1994,369:139-141, Chem.Eng.Sci.; 1977,33:315-318, Chem.Eng.Sci., 1996; 51:2649-2654, Ind.Eng.Chem.Res., 1993,32:2580-2594); Wherein (Selective Catalytic Reduction is to use wider technology in thermal power plant at present SCR) to selective catalytic reduction, is prone to poison but SCR method major defect is a catalyst, and ammonia leakage and investment and operating cost are too high (sees document Heck; H, M., Farrauto, R.J.Catalytic Air Pollution Control:Commercial Technology; Van Nostrand Reinhold:New York, 1995).
In recent years, the researcher finds that transition metal such as iron, cobalt, nickel can form the complex compound of π-sour ligand with NO, and nowadays ferrous complexing agent and cobalt complexing agent desulphurization denitration simultaneously are this technological main flows.
Application number is 01105004.7; 01105698.3; 02110646.0 200310108514.0 one Chinese patent application discloses the method for NO in cobalt ammonia solution and the triethylenediamine cobalt solution efficient absorption flue gas, the concentration of NO is minimum in working off one's feeling vent one's spleen can reach 0%; Wherein triethylenediamine cobalt is prone to regeneration, and tool advantage.But owing to there is a large amount of SO in the flue gas 2, SO 2Hydrolysis generates SO 3 2-, be prone to form Co with triethylenediamine cobalt 2(SO 3) 3Precipitate, reduced the content of active component.Application number is that 200510100019.4 Chinese patents disclose urea and triethylenediamine cobalt (III) and unite and remove SO in the flue gas 2With the method for NO, but with urea (NH 2) 2CO is that desulfurization material can produce greenhouse gases CO 2, used cobalt is the trivalent cobalt.Application number 02110646.0 discloses the denitrogenation of triethylenediamine cobalt (II) co-oxidation calcium desulfurizing, removes SO with calcium oxide 2Generate calcium sulfite, but the calcium sulfite benefit is low, causes to reclaim the sulphur resource, is prone to cause the obstruction of equipment and the secondary pollution of solid waste simultaneously.Ethylenediamine high volatility in addition.
Summary of the invention
Basic principle of the present invention is: the soda of adding at first with flue gas in SO 2Reaction generates sodium sulfite (Na 2SO 3), shown in the following reaction equation (1).The citric acid of flue gas after desulfurization entering subsequently closes in the blend absorbent of cobalt (II) and soda; NO in this absorption liquid in the flue gas is nitrite anions and nitrate anion by the liquid complexing catalytic oxidation; Following reaction equation (2)-(6)) shown in; Nitrite anions that generates and the reaction of the soda in nitrate anion and the absorption liquid generate natrium nitrosum and sodium nitrate, shown in the following reaction equation (7), then sodium sulfite and natrium nitrosum liquid are carried out forced oxidation acquisition sodium sulphate and sodium nitrate respectively; Shown in following reaction equation (8)-(9), after crystallization and drying.Wherein the cit in the reaction equation representes citric acid.
SO 2+Na ++H 2O→Na 2SO 3?(1)
NO(g)→NO(aq) (2)
[Co(cit) 3] 2++NO(aq)+OH -→[Co(cit) 2(NO)(OH)] ++en (3)
2[Co(cit) 2(NO)(OH)] ++O 2→2[Co(cit) 2(NO 2)(OH)] + (4)
2[Co(cit) 2(NO 2)(OH)] ++4OH_→2[Co(cit) 2(OH) 2]+NO 2 -+NO 3 -+H 2O?(5)
[Co(cit) 2(OH) 2]+cit→[Co(cit) 3] 2++2OH - (6)
NO 2 -+NO 3 -+Na ++H 2O→NaNO 2+NaNO 3 (7)
2Na 2SO 3+O 2→2Na 2SO 4 (8)
2NaNO 2+O 2→2NaNO 3 (9)
Implementation of the present invention is:
At first in desulfurizing tower, adopt the flue gas desulfurization of soda method, remove the SO in the flue gas 2, the flue gas after the desulfurization gets in the denitration absorption tower, in the denitration absorption tower, closes cobalt and soda mixed liquor work spray absorption liquid with the citric acid for preparing, and in this absorption tower, accomplishes denitration.Respectively with all oxidations of the absorption liquid after desulfurization and the denitration, obtain sodium sulphate and sodium nitrate then.
Being controlled between the 5-7 in the pH of desulfurization stage value described in the scheme, liquid-gas ratio is 1-20L/m 3Between, absorption temperature is controlled between 40-80 ℃, SO in the flue gas 2Concentration is no more than 4000ppm, and the Na ion concentration mass percent is in the soda absorption liquid: 0.3%-6%; Denitration stage pH value is controlled between the 7-11, and liquid-gas ratio is controlled at 1-25L/m 3Between; NO concentration is no more than 1000ppm; The citric acid percent by volume is: 0.1%-3%, the molar concentration that the citric acid that inorganic inferior cobalt salt and citric acid complex form closes cobalt is: 0.005-0.25mol/L, the Na ion concentration mass percent is in the soda absorption liquid: 0.3%-6%.
The present invention and existing desulphurization denitration compared with techniques have following advantage:
(1) realizes SO 2With the NO resource.Adopt soda-citric acid to close the cobalt desulphurization denitration, can realize SO 2Be separately converted to sodium sulphate and sodium nitrate with NO, thereby realize SO 2Resource with NO.Overall reaction is:
2NO+2SO 2+3H 2O+6Na ++O 2=2NaNO 3+2Na 2SO 4
This method is different from general denitration, and NO is converted into N 2
(2) develop a kind of new flue-gas denitration process.Scope of application denitrating technique the widest, that the smoke treatment amount is big mainly is SCR both at home and abroad at present, and this kind technology investment is big, operating cost is high, and the reaction principle of employing is a gas-solid-phase catalytic reaction, and reaction temperature is high, and resistance to mass tranfer is big, and efficient is low.And this process using is traditional absorption process technology, reaction temperature low (normal temperature), and resistance to mass tranfer is little, and efficient is high.
(3) citric acid closes cobalt regeneration of absorption solution solution, and citric acid closes cobalt does not need complicated regenerative system.
(4) operating condition is gentle, carries out at normal temperatures and pressures, and the desulphurization denitration rate is high, small investment, and operating cost is low.
Description of drawings
Figure is that soda-citric acid closes cobalt desulfuring and denitrifying apparatus and process chart simultaneously
The specific embodiment
Below in conjunction with embodiment the present invention is further set forth, but the present invention not only limits to following embodiment.
Embodiment 1
The flue gas desulfurization and denitrification test is being carried out as in the device shown in the drawings, and spray column is diameter phi 75mm, high 100mm glass spray column, and the gas-liquid two-phase adverse current, gas flow is 30m in desulfurizing tower 3/ h, the 120L/h of liquid-absorbent liquid, temperature is 50 ℃, the pH value is 5.5, SO 2Entrance concentration is 2100ppm, and the mass concentration of sodium ion is 5%; Gas flow is 30m in denitrating tower 3/ h, the liquid spraying amount is 100L/h, and temperature is 40 ℃, and the pH value is 8, and the NO entrance concentration is 800ppm, and the concentration of sodium ion is 6%, and it is 0.10mol/L that citric acid closes cobalt concentration.SO in the flue gas 2Import and export concentration with NO and measure, stable back outlet SO with the KM940 of Britain Kain Co., Ltd. flue gas analyzer 2Concentration is 100ppm, and desulfurization degree is 95.2%, and the NO exit concentration is 75ppm, and removal efficiency is 90.6%.
Embodiment 2
Experimental rig is identical with embodiment 1 with the desulfurization operations condition, just changes the operating condition of denitrating tower, and gas flow is 30m in denitrating tower 3/ h, the liquid spraying amount is 100L/h, and temperature is 40 ℃, and the pH value is 10, and the NO entrance concentration is 800ppm, and the concentration of sodium ion is 6%, and it is 0.10mol/L that citric acid closes cobalt concentration.Stable back outlet SO 2Concentration is 100ppm, and desulfurization degree is 95.2%, and the NO exit concentration is 46ppm, and removal efficiency is 94.3%.
Embodiment 3
Experimental rig is identical with embodiment 1, and gas flow is 20m in desulfurizing tower 3/ h, the 80L/h of liquid-absorbent liquid, temperature is 50 ℃, the pH value is 6, SO 2Entrance concentration is 3000ppm, and the concentration of sodium ion is 6%; Gas flow is 20m in denitrating tower 3/ h, the liquid spraying amount is 60L/h, and temperature is 40 ℃, and the pH value is 10, and the NO entrance concentration is 600ppm, and the concentration of sodium ion is 6%, and it is 0.15mol/L that citric acid closes cobalt concentration.SO in the flue gas 2Import and export concentration with NO and measure, stable back outlet SO with the KM940 of Britain Kain Co., Ltd. flue gas analyzer 2Concentration is 102ppm, and desulfurization degree is 96.6%, and the NO exit concentration is 60ppm, and removal efficiency is 90%.
Embodiment 4
Experimental rig is identical with embodiment 1, and gas flow is 50m in desulfurizing tower 3/ h, the 300L/h of liquid-absorbent liquid, temperature is 50 ℃, the pH value is 5, SO 2Entrance concentration is 2500ppm, and the concentration of sodium ion is 5%; Gas flow is 50m in denitrating tower 3/ h, the liquid spraying amount is 200L/h, and temperature is 40 ℃, and the pH value is 9, and the NO entrance concentration is 1000ppm, and the concentration of ammonia is 6%, and it is 0.2mol/L that citric acid closes cobalt concentration.SO in the flue gas 2Import and export concentration with NO and measure, stable back outlet SO with the KM940 of Britain Kain Co., Ltd. flue gas analyzer 2Concentration is 65ppm, and desulfurization degree is 97.4%, and the NO exit concentration is 95ppm, and removal efficiency is 90.5%.

Claims (6)

1. one kind is adopted soda and citric acid to close the method that cobalt (II) wet flue gas while desulphurization denitration is produced sodium sulphate and sodium nitrate, it is characterized in that: in desulfurizing tower, adopt the flue gas desulfurization of soda method, remove the SO in the flue gas 2Flue gas after the desulfurization gets in the denitration absorption tower, in the denitration absorption tower, closes cobalt and soda mixed liquor work spray absorption liquid with the citric acid for preparing, and in this absorption tower, accomplishes denitration; Respectively with all oxidations of the absorption liquid after desulfurization and the denitration, obtain sodium sulphate and sodium nitrate then.
2. method according to claim 1, it is characterized in that in desulfurization the Na ion concentration mass percent is in the soda absorption liquid: between the 0.3%-6%, liquid-gas ratio is: 1-20L/m 3Between, the pH value is controlled between the 5-7, SO in the flue gas 2Concentration is no more than 4000ppm, and absorption temperature is between 40-80 ℃.
3. method according to claim 1; It is characterized in that what denitration absorbing liquor was made up of citric acid, inorganic inferior cobalt salt and soda; The citric acid percent by volume is: 0.1%-3%, the molar concentration that the citric acid that inorganic inferior cobalt salt and citric acid complex form closes cobalt is: 0.005-0.25mol/L.
4. method according to claim 3 is characterized in that described inorganic inferior cobalt salt is: cobalt chloride, the inferior cobalt of sulfuric acid or colbaltous nitrate.
5. method according to claim 1, it is characterized in that described denitration operating condition is: denitration stage pH value is controlled between the 7-11, and liquid-gas ratio is controlled at 1-25L/m 3Between, NO concentration is no more than 1000ppm, in the denitration absorber portion in the soda absorption liquid Na ion concentration mass percent be: 0.3%-6%.
6. method according to claim 1 is characterized in that in desulfurizing tower and denitrating tower bottom respectively the forced oxidation all of the absorption liquid after desulfurization and the denitration, and through evaporative crystallization acquisition sodium sulphate and sodium nitrate.
CN2012101678592A 2012-05-28 2012-05-28 Method for producing sodium sulfate and sodium nitrate by simultaneous desulfurization and denitrification by soda-citric acid cobalt (II) CN102698581A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2012101678592A CN102698581A (en) 2012-05-28 2012-05-28 Method for producing sodium sulfate and sodium nitrate by simultaneous desulfurization and denitrification by soda-citric acid cobalt (II)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2012101678592A CN102698581A (en) 2012-05-28 2012-05-28 Method for producing sodium sulfate and sodium nitrate by simultaneous desulfurization and denitrification by soda-citric acid cobalt (II)

Publications (1)

Publication Number Publication Date
CN102698581A true CN102698581A (en) 2012-10-03

Family

ID=46891805

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2012101678592A CN102698581A (en) 2012-05-28 2012-05-28 Method for producing sodium sulfate and sodium nitrate by simultaneous desulfurization and denitrification by soda-citric acid cobalt (II)

Country Status (1)

Country Link
CN (1) CN102698581A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103331095A (en) * 2013-07-16 2013-10-02 国家海洋局天津海水淡化与综合利用研究所 Simultaneous desulphurization and denitration device for seawater smoke with membrane absorption method, as well as process of device
CN104190220A (en) * 2014-08-27 2014-12-10 袁磊 Device and method for denitrifying flue gas of coking furnace
CN104607029A (en) * 2015-01-23 2015-05-13 大连理工大学 Synchronous flue gas desulfurization and denitrification process combining chemical absorption with anaerobic-aerobic conversion
CN109908716A (en) * 2019-02-22 2019-06-21 浙江大学 A kind of compound additive and application for the collaboration denitration of magnesium basis wet method sulfur removal technology
CN110124451A (en) * 2019-05-13 2019-08-16 上海大学 SO in wet type substep removing flue gas2With the method for NO

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3978005A (en) * 1973-08-01 1976-08-31 Nissan Motor Co., Ltd. Catalyst for contact reduction of NOx in engine exhaust gases and method of producing same
CN1544126A (en) * 2003-11-11 2004-11-10 华东理工大学 Method for removing and reclaiming NO and SO2 in waste gas using ammonia solution
CN101664694A (en) * 2008-09-04 2010-03-10 北京石油化工学院 Catalyst for decomposition of N2O and preparation method and application thereof
CN101810996A (en) * 2010-04-30 2010-08-25 成都信息工程学院 Method for producing ammonium sulfate and ammonium nitrate by simultaneously desulfurizing and denitrating ammonia water and cobaltic ethylenediamine (II)
CN102350197A (en) * 2011-07-11 2012-02-15 华东理工大学 Fume desulfurizing and denitrifying device based on magnesia and method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3978005A (en) * 1973-08-01 1976-08-31 Nissan Motor Co., Ltd. Catalyst for contact reduction of NOx in engine exhaust gases and method of producing same
CN1544126A (en) * 2003-11-11 2004-11-10 华东理工大学 Method for removing and reclaiming NO and SO2 in waste gas using ammonia solution
CN101664694A (en) * 2008-09-04 2010-03-10 北京石油化工学院 Catalyst for decomposition of N2O and preparation method and application thereof
CN101810996A (en) * 2010-04-30 2010-08-25 成都信息工程学院 Method for producing ammonium sulfate and ammonium nitrate by simultaneously desulfurizing and denitrating ammonia water and cobaltic ethylenediamine (II)
CN102350197A (en) * 2011-07-11 2012-02-15 华东理工大学 Fume desulfurizing and denitrifying device based on magnesia and method

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103331095A (en) * 2013-07-16 2013-10-02 国家海洋局天津海水淡化与综合利用研究所 Simultaneous desulphurization and denitration device for seawater smoke with membrane absorption method, as well as process of device
CN103331095B (en) * 2013-07-16 2015-01-14 国家海洋局天津海水淡化与综合利用研究所 Simultaneous desulphurization and denitration device for seawater smoke with membrane absorption method, as well as process of device
CN104190220A (en) * 2014-08-27 2014-12-10 袁磊 Device and method for denitrifying flue gas of coking furnace
CN104607029A (en) * 2015-01-23 2015-05-13 大连理工大学 Synchronous flue gas desulfurization and denitrification process combining chemical absorption with anaerobic-aerobic conversion
CN109908716A (en) * 2019-02-22 2019-06-21 浙江大学 A kind of compound additive and application for the collaboration denitration of magnesium basis wet method sulfur removal technology
CN110124451A (en) * 2019-05-13 2019-08-16 上海大学 SO in wet type substep removing flue gas2With the method for NO

Similar Documents

Publication Publication Date Title
Zhang et al. Simultaneous removal of NO and SO2 from flue gas by ozone oxidation and NaOH absorption
CN104941423B (en) A kind of regeneration fume from catalytic cracking ammonia process of desulfurization denitration dust collecting method and device
CN102247750B (en) Method for simultaneously desulfurizing and denitrifying flue gas by ozone catalytic oxidation process
CN101745305B (en) Method for removing various gaseous pollutants from smoke gas
CN104801178B (en) Method for simultaneously desulfurizing, denitrifying and removing mercury by combining radical pre-oxidation with wet absorption
CN102343212B (en) Denitration process combining co-oxidation of ozone and hydrogen peroxide with wet absorption
CN102527205B (en) Method and system for simultaneously removing sulfur, niter and mercury from smoke based on catalytic oxidation
CN103657368B (en) A kind of simultaneous SO_2 and NO removal demercuration dry-method fume gas purification method and device
CN102716648B (en) Method for automatically controlling desulphurization and denitration by flue gas based on pH value and ORP value and apparatus thereof
CN102489129B (en) Industrial flue gas purification, desulfurization and denitrification integrated device and working method thereof
CN103706238B (en) System and method for removing SO2, NO and Hg in smoke on the basis of heterogeneous Fenton
CN103331095B (en) Simultaneous desulphurization and denitration device for seawater smoke with membrane absorption method, as well as process of device
CN1192814C (en) Method for urea catalyst simultaneously processing flue gas and desulfurizing denitrification
CN102350197B (en) Fume desulfurizing and denitrifying device based on magnesia and method
CN101711991B (en) Fe molecular sieve composite catalyst and preparation method thereof
CN102049257B (en) Catalyst for simultaneously reducing SO2 and NO with CO as well as preparation and application of catalyst
Zheng et al. Nitrogen oxide absorption and nitrite/nitrate formation in limestone slurry for WFGD system
CN103230733B (en) The device of a kind of liquid phase catalytic oxidation flue gas desulfurization and denitrification integration and technique
CN105478133B (en) A kind of low cost SCR denitration catalyst and preparation method thereof
CN101648107A (en) Catalytic oxidation adsorption desulfurizer and preparation method thereof
CN101279185B (en) Gas phase oxidation-liquid phase reduction method for absorbing and removing nitrous oxides in exhaust air
CN104056658B (en) Low-temperature sulfur-resistant denitration catalyst and preparing method thereof
CN103894047B (en) Flue gas pollutant controls integrated purifying recovery process
CN103721553A (en) Method for efficiently removing acid gas sulfide by ammonia process desulfurization technique
CN102824844A (en) Desulfurization and denitrification agent, preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20121003

C02 Deemed withdrawal of patent application after publication (patent law 2001)