CN102527325B - Aluminum-modified attapulgite adsorbent and preparation method and application - Google Patents
Aluminum-modified attapulgite adsorbent and preparation method and application Download PDFInfo
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- CN102527325B CN102527325B CN201010582513.XA CN201010582513A CN102527325B CN 102527325 B CN102527325 B CN 102527325B CN 201010582513 A CN201010582513 A CN 201010582513A CN 102527325 B CN102527325 B CN 102527325B
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- tetracyclines
- attapulgite
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Abstract
The invention discloses an aluminum-modified attapulgite adsorbent and a preparation method and application. Aluminum element content in the aluminum-modified attapulgite adsorbent is 4.0-8.5% by weight percentage. Added dissolvable aluminum compound is one or a plurality of sulfate, nitrate, chlorate and poly-aluminum. The preparation method includes steps of: (1) purification of attapulgite and (2) modification of the purified attapulgite. The aluminum-modified attapulgite adsorbent can be used for treating compounds of tetracyclines in medicine sewage. The aluminum-modified attapulgite adsorbent, the preparation method and application have the advantages of: (1) being capable of being used directly without performing acid and alkali adjustment on tetracyclines solutions and being easy and convenient to operate; (2) improving adsorption rate and improving adsorption performance; and (3) capable of leading adsorption removing rate of tetracyclines to be reach 93%, and leading removing rate of tetracyclines solution to achieve 100% when concentration is 5-20mg/L. The aluminum-modified attapulgite adsorbent, the preparation method and application can be applied to tetracyclines treatment of domestic sewage, medical waste water, surface water and the like.
Description
Technical field
The present invention relates to the sewage treatment area in environmental protection, particularly relate to a kind of for the aluminium modified attapulgite adsorbent in medical sewage disposal and method for making and application.
Background technology
TCs (tetracycline antibiotics, TCs, hereinafter to be referred as Tetracyclines) be the class broad-spectrum antibiotic being produced by streptomycete, frequency of utilization is high, scope is wide, be mainly used in treating infectious diseases, also by a large number for animal husbandry and aquaculture, in addition, in food industry, be used as antimicrobial growth promoter and accelerate the growth of animal.It is reported, this type of antibiotics production and use amount world rankings the second, China ranks the first.Tetracyclines comprises natural Tetracyclines and semi-synthetic Tetracyclines, natural Tetracyclines is the antibiotic extracting from Streptomyces nutrient solution, as terramycin, tetracycline and aureomycin, semi-synthetic Tetracyclines is to carry out structure of modification to obtain take natural Tetracyclines as raw material, as Doxycycline be take terramycin as raw material after the multistep chemical reactions such as chloro, dehydration, hydrogenation salify and displacement, then by purification, decolouring, filtration, crystallization and dry making.
Nineteen fifty FDA (FAD) ratifies antibiotic first as after feed addictive, and countries in the world are in succession applied to antibiotic herding and produce, and have promoted large-scale cultivation.China since early 1990s, Tetracyclines extensive use in the industries such as medicine, animal husbandry and aquaculture, its output and consumption are always in rising trend.But its production in above-mentioned industry and use and a large amount of waste water of producing are unprocessed or process and thoroughly do not make Tetracyclines enter ecological environment with water, therefore, the content of Tetracyclines in water environment grows with each passing day, and the negative effect of the mankind and ecological environment is also highlighted day by day.
For the ecosystem, abuse Tetracyclines can directly cause individual drug resistance.Research shows, in environment, the Tetracyclines resistance of some bacteriums, far away higher than expection, shows that the drug resistance gene of bacterium may transfer occur at occurring in nature.The drug resistance of Tetracyclines may pass to malignant bacteria from non-pathogenic bacteria, even may further propagate, and develops into the drug resistance on ecological level, makes not have the individuality that directly contacts Tetracyclines also to produce drug resistance.
Residual composition and the activity that can affect microorganisms in water of Tetracyclines in water environment, thus microbial ecological structure changed, and nitrated, the mineralization and the soil nutrient that affects soil circulate.In addition, the residual of Tetracyclines also can impact plant, aquatic animal and geobiont etc., because the difference of residual concentration produces the harm such as growth inhibition, variation and teratogenesis.Because tetracycline compound can be through the lipophilic group of cell membrane, and there is higher stability, therefore, be easy to bioaccumulation and in environment long-term stable existence etc., thereby toxicity and the harmfulness of aggravating it.
For reducing the ecological risk of tetracycline compound in water environment, need to remove the tetracycline compound in sewage or high concentration surface water body.Conventional method for treating water has at present: the combination treatment method of physics, chemistry and bioanalysis and said method, but due to tetracycline compound complex structure, the conventional water treatment process of Sewage Plant is difficult to it to remove, and residual Tetracyclines makes the further biological treatment of sewage become difficulty in addition and efficiency is low.Compared with above-mentioned processing method, adsorption treatment has the advantages such as technique is simple, treatment effect stable, cheap.
Conventional sorbing material comprises active carbon, activated sludge, clay class etc., active carbon is a kind of high-performance sorbing material, patent publication No. CN101333011 has introduced a kind of method of utilizing tetracycline in mesoporous carbon Adsorption water, patent publication No. CN101337706 utilizes Powdered Activated Carbon to process the method for water body containing tetracycline antibiotics, two kinds of methods all have higher eliminating rate of absorption to tetracycline compound, absolutely prove the high absorption property of active carbon, but remove to as if single tetracycline compound, and active carbon is higher as sorbing material preparation cost, be difficult to apply, in Wastewater Treated by Activated Sludge Process water, when Tetracyclines, along with the increase of Tetracyclines concentration in water, eliminating rate of absorption reduces and generation is had in a large number drug-fast microorganism by processing procedure, will form potential danger after entering environment, soil class sorbing material because of cheap, kind is many, becomes the focus of current research.
The natural soil class sorbing material adopting about the absorption research of Tetracyclines both at home and abroad comprises clay, black grid soil, red soil etc., also there is the modification of employing composite adsorbing material as montmorillonite, bentonite/active carbon, zeroth order aluminium, modified corn straw etc., but natural soil class sorbing material exists adsorption capacity low, adsorption concentration is limited in scope, and is not suitable for removing tetracycline compound in high concentration water body.Patent publication No. CN101249417 has introduced Concave-convex clay rod-aluminium hydroxide/aluminium nano-compound adsorbent, its preparation method and application, utilize aluminium/iron modified attapulgite clay, compound adsorbent after modification has high-adsorption-capacity to phosphorus, As, F in water, can be for the processing of the advanced treating dephosphorization of sanitary sewage disposal factory draining, eutrophication water dephosphorization, high arsenic or high fluorine groundwater, but this kind of modification require aluminium, iron simultaneously with addition of, complicated operation, and compound adsorbent after modification is studied at absorption Tetracyclines.
Summary of the invention
The present invention is for avoiding the existing weak point of above-mentioned prior art, provides a kind of aluminium modified attapulgite adsorbent of high adsorption efficiency, for the treatment of tetracycline compound in waste water.
The present invention provides the preparation method of adsorbent simultaneously.
One of the present invention's aluminium modified attapulgite adsorbent is achieved in that
In described aluminium modified attapulgite adsorbent, aluminium element content is 4.0-8.5% by weight percentage, preferably 4.5-7.5%;
What the aluminium modifier adding in described aluminium modified attapulgite adsorbent was aluminium easily dissolves compound.
In concrete enforcement
Easily the dissolving compound and can be selected from one or more in sulfate, nitrate, chloride salt, polymeric aluminum of described aluminium.More preferably the compound that easily dissolves of aluminium is AlCl
36H
2o.
The preparation method of the present invention's two aluminium modified attapulgite adsorbent is achieved in that
Described method for making comprises the steps:
(1) attapulgite is purified
A. former attapulgite pulverizing, grinding are obtained to particle diameter≤100 object powder;
B. in concave and convex rod stone powder, add water, be made into the suspension that concentration is 5-10wt%, stir, concave and convex rod stone powder is uniformly dispersed;
C. in the suspension after dispersion treatment, add calgon, the mass ratio of itself and attapulgite is (1-5): 100, stir 0.5h, and ultrasonic 1h, leaves standstill 2h, dewaters to mud cake shape, 105 ℃ of dry 3h, the attapulgite after being purified;
(2) Concavo-convex and excellent after purifying stone modification
A. in the attapulgite after 5g being purified, add 150-200mL water, stir, the concave and convex rod stone powder after purifying is uniformly dispersed,
B. add the AlCl of 0.3-5.0g
36H
2o,
C. add the HCl of appropriate 1mol/L or the NaOH of 1mol/L that pH value is adjusted to neutrality,
D. magnetic agitation 2-3h, centrifuge washing 2-3 time, dries 36-48h for 40 ℃, grinds and obtains particle diameter≤100 object aluminium modified attapulgite adsorbent.
The present invention's three is the application in the tetracycline compound of processing in waste water of aluminium modified attapulgite adsorbent.
The present invention removes the impurity in attapulgite raw ore by purification, is regulated and is made aluminium modified attapulgite adsorbent by aluminium salt hydrolysis and pH value, makes aluminium hydroxide be attached to the attapulgite fibre bundle surface after purification.
Compared with the prior art, this technology beneficial effect is embodied in:
1, attapulgite is a kind of natural clay mineral, has unique layer chain crystal structure and very tiny (approximately 0.01 μ m × 1 μ bar-shaped, fibrous crystal form and larger specific area m).By purifying, remove the impurity in raw ore, attapulgite is uniformly dispersed; By aluminium modification, make attapulgite generation ion-exchange, Si
4+by Al
3+substitute Mg
2+by Al
3+substitute, the synthesis result of various ion substitutions is that attapulgite is usually electronegative, and this kind of electric charge belongs to structure charge, is generally that Tetracyclines cation carrys out balance by the low price macrocation that is arranged in duct; The hydroxide of aluminium salt hydrolysis generation aluminium is graininess and is wrapped in attapulgite fibre bundle surface, can there is irreversible chemisorbed with Tetracyclines in the hydroxide of aluminium, Tetracyclines is adsorbed with the attapulgite particle of electric charge and the hydroxide of aluminium simultaneously, improve the rate of adsorption, increase absorption property.
2, Tetracyclines is owing to containing many hydroxyls, enolic hydroxyl and carbonyl in molecule, therefore can generate infusible precipitate (generating yellow infusible precipitate with aluminium ion) with multiple polyvalent metal ion generation chelation in High-pH solution.It is acid that Tetracyclines solution is, attapulgite after modification is regulated and is made it be neutral by pH value, both approach the optimal pH scope that Tetracyclines is adsorbed for the mixed liquor of reaction, therefore, aluminium modified attapulgite adds Tetracyclines solution to reach the suitable environment that Tetracyclines is adsorbed, without Tetracyclines solution being carried out to acid, alkali adjusting, can directly come into operation, easy and simple to handle.
3, the adsorbent that prepared by the inventive method can effectively be removed the Tetracyclines of middle low concentration in water, with low cost, is the 5-10% of active carbon expense.The present invention proves by experiment, and when the concentration of the Tetracyclines aqueous solution is 5-150mg/L, aluminium modified attapulgite can reach more than 93% the eliminating rate of absorption of Tetracyclines, and when concentration is 5-20mg/L, eliminating rate of absorption part can reach 100%.Therefore, the present invention can be applicable to the processing of sanitary sewage, pharmaceutical wastewater, surface water etc.
Accompanying drawing explanation
Fig. 1 is aluminium modified attapulgite adsorbent transmission electron microscope picture of the present invention
Fig. 2-Fig. 7 is the impacts of different adsorption conditionses on eliminating rate of absorption.Wherein:
Fig. 2 is the affect schematic diagram of time on eliminating rate of absorption
Fig. 3 is the affect schematic diagram of TCs initial concentration on eliminating rate of absorption
Fig. 4 is the affect schematic diagram of temperature on eliminating rate of absorption
Fig. 5 is the affect schematic diagram of pH on eliminating rate of absorption
Fig. 6 is the affect schematic diagram of oscillation rate on eliminating rate of absorption
Fig. 7 is that different aluminum amount modified attapulgite adsorbent affects schematic diagram to eliminating rate of absorption
the specific embodiment
Below in conjunction with instantiation, invention is described in detail.Scope of the present invention is not limited with the specific embodiment, but is limited by the scope of claim.
Embodiment 1
In 150mL distilled water, add 10g particle diameter≤100 order attapulgite, stir, add 0.3g calgon after being uniformly dispersed, stir 0.5h, ultrasonic 1h, leaves standstill 2h, dewater to mud cake shape, and 105 ℃ of dry 3h, the attapulgite clay after being purified.
The attapulgite taking after 5g purifies is placed in 500mL beaker, adds 250mL distilled water, after magnetic agitation 0.5h, adds the AlCl of 0.894g
36H
2o (being equivalent to 0.10gAl), magnetic agitation 30min, guarantees AlCl
36H
2o dissolves completely, regulates pH value=7, continues stirring 1h, after centrifuge washing 3 times, in 40 ℃ of dry 36-48h, is ground to particle diameter≤100 order, makes aluminium modified attapulgite adsorbent.
The TEM figure that has shown composite in Fig. 1, prepared aluminium hydroxide is wrapped in attapulgite fibrous surfaces with graininess.
Accurate weighing is through aluminium modified attapulgite adsorbent 0.1000g (± 0.0005g), be placed in 250mL tool plug conical flask, adding 20mL concentration is in the Tetracyclines solution of 100mg/L, be placed in constant temperature oscillator, the rate oscillation of 150r/min at 25 ℃ of temperature, get supernatant and cross respectively the miillpore filter of 0.45 μ m at 1h, 3h, 6h, 12h, 24h, test residual Tetracyclines concentration by liquid chromatogram, three groups of each experiment settings are parallel, result is with arithmetic average value representation, and calculate standard deviation, guarantee measuring accuracy.As calculated, after terramycin, tetracycline, aureomycin, Doxycycline absorption 24h, clearance is respectively 93.2%, 94.1%, 97.1%, 97.7%.
Accompanying drawing 2, the impact of time on TCs eliminating rate of absorption.
Visible, aluminium modified attapulgite adsorbent has higher eliminating rate of absorption to four of Tetracyclines kinds of compounds, and eliminating rate of absorption has reached more than 80% at 3h, growth in time, clearance increases gradually, and after adsorption equilibrium, eliminating rate of absorption is all more than 93%.Adsorbing the preferred time is 3-24h.
Make aluminium modified attapulgite adsorbent with embodiment 1.
Accurate weighing is through aluminium modified attapulgite adsorbent 0.1000g (± 0.0005g), be placed in 250mL tool plug conical flask, add that 20mL concentration is respectively 10,20,50, in the Tetracyclines solution of 100mg/L, be placed in constant temperature oscillator, at 25 ℃ of temperature, the rate oscillation 24h of 150r/min is to adsorption equilibrium, get supernatant and cross the miillpore filter of 0.45 μ m, test residual four kinds of Tetracyclines concentration by liquid chromatogram, three groups of each experiment settings are parallel, result is with arithmetic average value representation, and calculate standard deviation, guarantee measuring accuracy.As calculated, terramycin, tetracycline, aureomycin, Doxycycline eliminating rate of absorption all reach more than 93%, and low concentration can reach 100% eliminating rate of absorption.
Accompanying drawing 3, the impact of TCs initial concentration on eliminating rate of absorption.
Visible, aluminium modified attapulgite adsorbent has very high clearance to the Tetracyclines water body of 5-150mg/L concentration.
Embodiment 3
Make aluminium modified attapulgite adsorbent with embodiment 1.
Accurate weighing is through aluminium modified attapulgite adsorbent 0.1000g (± 0.0005g), be placed in 250mL tool plug conical flask, adding 20mL concentration is in the Tetracyclines solution of 100mg/L, be placed in constant temperature oscillator, respectively at 5,15,25,40 ℃ of temperature the rate oscillation 24h of 150r/min to adsorption equilibrium, get supernatant and cross the miillpore filter of 0.45 μ m, test residual Tetracyclines concentration by liquid chromatogram, three groups of each experiment settings are parallel, result is with arithmetic average value representation, and calculate standard deviation, guarantee measuring accuracy.As calculated, terramycin, tetracycline, aureomycin, Doxycycline eliminating rate of absorption are all more than 90%.
Accompanying drawing 4, the impact of temperature on eliminating rate of absorption.
Visible, aluminium modified attapulgite adsorbent absorption tetracycline compound temperature influence is little, is applicable to the removal that the 0-50 ℃ of water body Tetracyclines under temperature conditions pollutes.
Make aluminium modified attapulgite adsorbent with embodiment 1.
Accurate weighing is through aluminium modified attapulgite adsorbent 0.1000g (± 0.0005g), be placed in 250mL tool plug conical flask, adding 20mL concentration is in the Tetracyclines solution of 100mg/L, regulator solution pH value is respectively 1,3,5,7,9 and is placed in constant temperature oscillator, at 25 ℃ of temperature, the rate oscillation 24h of 150r/min is to adsorption equilibrium, get supernatant and cross the miillpore filter of 0.45 μ m, test residual Tetracyclines concentration by liquid chromatogram, three groups of each experiment settings are parallel, result is with arithmetic average value representation, and calculate standard deviation, guarantee measuring accuracy.As calculated, terramycin, tetracycline, aureomycin, Doxycycline many in the time that pH value is 3-7 clearance higher, aureomycin and Doxycycline are that 9 o'clock clearances still reach more than 90% in pH value.
Accompanying drawing 5, the impact of pH on eliminating rate of absorption.
Visible, pH is larger to Adsorption Effect, and preferred solution pH value scope is 3-7.
Embodiment 5
Make aluminium modified attapulgite adsorbent with embodiment 1.
Accurate weighing is through aluminium modified attapulgite adsorbent 0.1000g (± 0.0005g), be placed in 250mL tool plug conical flask, adding 20mL concentration is in the Tetracyclines solution of 100mg/L, be placed in constant temperature oscillator, at 25 ℃ of temperature, respectively with 0,50,100,150, the rate oscillation 24h of 200r/min is to adsorption equilibrium, get supernatant and cross the miillpore filter of 0.45 μ m, test residual Tetracyclines concentration by liquid chromatogram, three groups of each experiment settings are parallel, result is with arithmetic average value representation, and calculates standard deviation, guarantees measuring accuracy.As calculated, terramycin, tetracycline, aureomycin, Doxycycline eliminating rate of absorption are all higher than 90%.
Accompanying drawing 6 is the impact of oscillation rate on eliminating rate of absorption.
Visible, the instructions for use of aluminium modified attapulgite adsorbent absorption Tetracyclines is low, can directly add use.
The Concave-convex clay rod taking after 5g purifies is placed in 500mL beaker, adds 250mL distilled water, after magnetic agitation 0.5h, adds respectively the AlCl of 0.447g, 0.894g, 1.341g, 2.236g, 4.471g
36H
2o (being equivalent to respectively 0.05g, 0.10g, 0.15g, 0.25g, 0.50gAl), magnetic agitation 30min, guarantees AlCl
36H
2o dissolves completely, regulates pH value=7, continues stirring 1h, after centrifuge washing 3 times, in 40 ℃ of dry 36-48h, is ground to particle diameter≤100 order, makes the aluminium modified attapulgite adsorbent of different aluminum amount.
Accurate weighing is through aluminium modified attapulgite adsorbent 0.1000g (± 0.0005g) respectively, be placed in 250mL tool plug conical flask, adding 20mL concentration is in the Tetracyclines solution of 100mg/L, be placed in constant temperature oscillator, at 25 ℃ of temperature, with the rate oscillation 24h of 150r/min to adsorption equilibrium, get supernatant and cross the miillpore filter of 0.45 μ m, with liquid chromatogram test Tetracyclines residual concentration, three groups of each experiment settings are parallel, result is with arithmetic average value representation, and calculates standard deviation, guarantees measuring accuracy.As calculated, obtain the eliminating rate of absorption of terramycin, tetracycline, aureomycin and Doxycycline.Result shows, in the time that aluminium amount is 0.05-0.25g, eliminating rate of absorption is all more than 80%; In the time that aluminium amount is 0.05-0.15g, eliminating rate of absorption is all more than 93%.
Accompanying drawing 7, the impact of different aluminum amount modified attapulgite adsorbent on eliminating rate of absorption.
Comparative example 1～6
This research is special prepares Concave-convex clay rod-aluminium hydroxide/iron nano-compound adsorbent with preparation method described in patent publication No. CN101249417, and TCs is adsorbed to test.
Take 0.1000g (± 0.0005g) adsorbent and join in 20mL Tetracyclines solution, Tetracyclines initial concentration is 100mg/L, and adsorption time is 24h, oscillation rate 150r/min, 25 ℃ of temperature.Each experiment set three groups parallel, result is with arithmetic average value representation, and calculates standard deviation, guarantees measuring accuracy.
Result of the test shows:
With 10gAlCl
3adsorbent after modification 10g concave and convex rod stone powder to the clearance of terramycin, tetracycline, aureomycin, Doxycycline be followed successively by 54.3%/, 51.0%, 49.0%, 72.0%.
With described 5g AlCl
3with 5g FeCl
3the adsorbent of modification 10g concave and convex rod stone powder is followed successively by 59.3%, 58.6%, 58.0%, 51.6% to the clearance of terramycin, tetracycline, aureomycin, Doxycycline.
From experimental result, the attapulgite after above-mentioned two kinds of modifications is all not high to the eliminating rate of absorption of Tetracyclines, and practical application is restricted, and does not reach the efficient processing to Tetracyclines sewage.
Claims (2)
1. aluminium modified attapulgite adsorbent, processing the application in tetracycline compound in pharmaceutical wastewater, is characterized in that the method for making of described aluminium modified attapulgite adsorbent comprises the steps:
(1) attapulgite is purified
A. former attapulgite pulverizing, grinding are obtained to particle diameter≤100 object powder;
B. in concave and convex rod stone powder, add water, be made into the suspension that concentration is 5-10wt%, stir, concave and convex rod stone powder is uniformly dispersed;
C. in the suspension after dispersion treatment, add calgon, the mass ratio of itself and attapulgite is (1-5): 100, stir 0.5h, and ultrasonic 1h, leaves standstill 2h, dewaters to mud cake shape, 105 ℃ of dry 3h, the attapulgite after being purified;
(2) Concavo-convex and excellent after purifying stone modification
A. in the attapulgite after 5g being purified, add 150-200mL water, stir, the concave and convex rod stone powder after purifying is uniformly dispersed;
B. add the AlCl of 0.3-5.0g
36H
2o;
C. add the HCl of appropriate 1mol/L or the NaOH of 1mol/L that pH value is adjusted to neutrality;
D. magnetic agitation 2-3h, centrifuge washing 2-3 time, dries 36-48h for 40 ℃, grinds and obtains particle diameter≤100 object aluminium modified attapulgite adsorbent;
In described aluminium modified attapulgite adsorbent, aluminium element content is 4.0-8.5% by weight percentage.
2. application as claimed in claim 1, is characterized in that:
In described aluminium modified attapulgite adsorbent, aluminium element content is 4.5-7.5% by weight percentage.
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| CN103357376A (en) * | 2013-07-18 | 2013-10-23 | 淮阴工学院 | Nano-grade attapulgite substrate SO2 absorption agent preparation method |
| CN105709783B (en) * | 2016-01-21 | 2018-09-18 | 盐城工学院 | A kind of NH4F is modified TO2/ Al-ATP catalyst and its preparation method and application |
| CN105968414B (en) * | 2016-05-13 | 2018-11-23 | 江苏艾特克阻燃材料有限公司 | A kind of fire retardant and its method of modifying, fire proofing and preparation method thereof |
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| CN1843950A (en) * | 2006-04-24 | 2006-10-11 | 四川大学 | Method for preparing decoloring material of dyeing waste water by attapulgite ore |
| CN101249417A (en) * | 2008-03-28 | 2008-08-27 | 合肥工业大学 | Concave-convex bar stone clay-trihydrate alumina/iron nano composite adsorbing agent, preparation and applications |
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| CN1843950A (en) * | 2006-04-24 | 2006-10-11 | 四川大学 | Method for preparing decoloring material of dyeing waste water by attapulgite ore |
| CN101249417A (en) * | 2008-03-28 | 2008-08-27 | 合肥工业大学 | Concave-convex bar stone clay-trihydrate alumina/iron nano composite adsorbing agent, preparation and applications |
Non-Patent Citations (2)
| Title |
|---|
| Po-Hsiang Chang et al..Sorptive removal of tetracycline from water by palygorskite.《Journal of Hazardous Materials》.2008,第165卷第148-155页. |
| Sorptive removal of tetracycline from water by palygorskite;Po-Hsiang Chang et al.;《Journal of Hazardous Materials》;20081007;第165卷;第148-155页 * |
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Inventor after: Wang Jinsheng Inventor after: Li Jian Inventor after: Bao Wenju Inventor after: Teng Yanguo Inventor after: Zuo Rui Inventor before: Wang Jinsheng Inventor before: Li Jian Inventor before: Bao Wenju |
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Free format text: CORRECT: INVENTOR; FROM: WANG JINSHENG LI JIAN BAO WENJU TO: WANG JINSHENG LI JIAN BAO WENJU TENG YANGUO ZUO RUI |
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Granted publication date: 20140604 Termination date: 20191210 |