CN102989429B - Preparation method of cadmium ion surface imprint adsorbing material - Google Patents
Preparation method of cadmium ion surface imprint adsorbing material Download PDFInfo
- Publication number
- CN102989429B CN102989429B CN201210486758.1A CN201210486758A CN102989429B CN 102989429 B CN102989429 B CN 102989429B CN 201210486758 A CN201210486758 A CN 201210486758A CN 102989429 B CN102989429 B CN 102989429B
- Authority
- CN
- China
- Prior art keywords
- ion
- solution
- phema
- sio
- preparation
- 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
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a preparation method of an adsorbing material of metal ions in a water system and particularly relates to a preparation method of a cadmium ion surface imprint adsorbing material. The preparation method comprises the steps of placing functional grafting particles HQ-PHEMA (Hydroxyquinoline-Poly Hydroxyethyl Methylacrylate)/SiO2 into a Cd<2+> ion water solution with the concentration of 0.01 mol/L; adjusting the pH (Potential of Hydrogen) value of a solution system to 5.5 with a sodium hydroxide solution; placing the solution into a constant-temperature oscillator to carry out constant-temperature oscillation; filtering the particles and drying in vacuum; placing the functional grafting particles which are adsorbed with Cd<2+> ions in a saturated manner into a water and ethanol mixed solvent containing the Cd<2+> ions; utilizing the sodium hydroxide solution to adjust the pH value of the system; taking dichloroether as a cross-linking agent to react under the condition that the temperature is 40-50 DEG C for 20-26 hours to form a cross-linking imprint; utilizing a hydrochloric acid solution to repeatedly wash the product to remove template ions, namely the Cd<2+> ions; and drying in vacuum to form the Cd<2+> ion surface imprint adsorbing material.
Description
Technical field
The present invention relates to the preparation method of metal biosorption material in aqueous systems, be specifically related to a kind of preparation method of cadmium ion surface imprint sorbing material.
Background technology
Heavy metal cadmium is a kind of harmful environomental pollution source, it not only affects growing of crop, but also by biological concentration and eventually through food chain harm humans health, the cadmium of long-term excess intake, the absorption of other beneficial elements in human body can be affected, cause the problem such as endocrinopathy, poor appetite, insomnia, blood pressure rising.Cadmium poisoning can cause osteoporosis, softens and textured bone is fractured even dead.In addition, cadmium is also a kind of carcinogen, and IARC (IARC) divides I class carcinogenic substance into cadmium, and poisonous substance administration committee of the U.S. is classified as cadmium as the noxious material that the 6th is jeopardized health.Therefore process cadmium wastewater and eliminate cadmium pollution, exploitation efficient metal ion adsorbent has caused showing great attention to of the mankind.
At present, be separated and have multiple with the method removing cadmium ion in aqueous medium, as chemical precipitation method, chemical reduction method, ion-exchange, hyperfiltration, membrane separation process, biological treatment and absorption method, all methods are compared, absorption method due to its operation run easy, cost is low, removal efficiency is high, adsorbent also renewable with recycle, therefore, be a kind of effective method.But general solid absorbent is to the object ion in water body without recognition capability, and therefore suction-operated lacks selective, significantly limit the application of general absorption method.And with ion imprinted polymer material (Ion Imprinted Polymers, IIPs) time for heavy metal ion in sorbent treatment aqueous medium, then not only adsorption capacity is high, and has special adsorptive selectivity, is a kind of solid-liquid processing method efficiently.Application number is the preparation method and the application that disclose sponge gourd chromium surface lead ion trace sorbing material in the patent of 201010293780.5, and sponge gourd chromium surface ion blotting sorbing material lead ion maximal absorptive capacity is 335mg/g, and most high adsorption rate can reach 95%.[the Gulay Bayramoglu such as Gulay Bayramoglu, M. Yakup Arica. Journal of Hazardous Materials.2011, the maximum adsorption capacity of the ion surface imprinted material heavy metal Cr (VI) of the Cr (VI) 187 (1-3): 213] prepared is 3.31 mmol/g, repeatedly uses adsorption capacity to reduce.
Traditional imprinted polymer uses investment preparation, and device needed for the method is simple, and universality is strong, but there is following shortcoming: obtained is block imprinted polymer, and imprinting efficiency is not high; Pulverize, grind and sieve the process obtaining imprinted polymer particulate, operate comparatively numerous and diverse; And it is not many imprinted cavity are destroyed, and cause imprinted cavity Limited Number in particle, high to the binding ability of template (molecule) ion; In addition, the particulate obtained for presoma by block imprinted polymer, matrix is thicker, and the duct in hole is comparatively dark, and template (molecule) ion diffuse resistance is large, and mass transfer velocity is comparatively slow, is not easily combined with recognition site.
Summary of the invention
Technical problem to be solved by this invention is: provide the preparation method that a kind of preparation technology is simple, can have the cadmium ion surface imprint sorbing material of superelevation identification and adsorption capacity to cadmium ion.
The technical solution adopted in the present invention is: a kind of preparation method of cadmium ion surface imprint sorbing material, prepares as follows:
Step 1, saturated adsorption: by function grafting particulate HQ-PHEMA/SiO
2 (be bonded with poly hydroxy ethyl acrylate (the PHEMA)/SiO of oxine (HQ)
2) be placed in the Cd that concentration is 0.01 mol/L
2+deionized water solution, sodium hydroxide solution regulates the pH value of solution system to be 5.5, is placed in constant temperature oscillator, constant temperature oscillation, function grafting particulate HQ-PHEMA/SiO
2with cadmium ion (Cd
2+) between interaction after, filtering particles, vacuum drying, obtains saturated adsorption Cd
2+the function grafting particulate of ion;
Step 2, crosslinked trace: saturated adsorption Cd prepared by step one
2+the function grafting particulate of ion is placed in containing Cd
2+in the water of ion and alcohol mixed solvent, by the pH value of sodium hydroxide solution regulation system, take dichloroether as crosslinking agent, under temperature is 40 DEG C of-50 DEG C of conditions, the chlorine groups at dichloroether molecule two ends and function grafting particulate HQ-PHEMA/SiO
2quaternized between quinoline atom N on side chain carries out reaction 20-26 h, forms crosslinked trace;
Step 3, template removal: with hydrochloric acid solution cyclic washing step 2 product, to remove template ion Cd
2+ion, vacuum drying, leaves a large amount of Cd in the polymer foil of function grafting particulate
2+ion blotting hole, thus form Cd
2+ion surface imprinted sorbing material.
As a kind of preferred embodiment: function grafting particulate HQ-PHEMA/SiO in step one
2in the Cd of PHEMA grafting degree to be the bond densities of 30%-40%, HQ be 1.75mmol/g-1.85mmol/g, every 5L
2+the function grafting particulate HQ-PHEMA/SiO of 1g is put in deionized water solution
2 , the constant temperature oscillation time is 4 h.
As a kind of preferred embodiment: when in step 2, the mixed solvent of water and ethanol is prepared, the volume ratio of water and ethanol is 7:3, is 4.5-5.5 by the pH value of sodium hydroxide solution regulation system.
As a kind of preferred embodiment: use 0.1 molL in step 3
-1hydrochloric acid solution cyclic washing product particles.
The invention has the beneficial effects as follows: the imprinted cavity of imprinted polymer prepared by (1) the method is positioned at the top layer of imprinted polymer, fast in conjunction with speed to cadmium ion, identification selection superelevation, elution efficiency is high.With Cu
2+and Pb
2+thing as a comparison, imprinted material is to Cd
2+the selectivity factor of ion is respectively 25.52 and 22.91; And hole is not damaged in preparation process, binding capacity is high, can reach 0.44mmol/g.(2) preparation process of the present invention take silica gel as matrix, and mechanical strength is large, is applicable to the requirement of suitability for industrialized production.Preparation process is simple, and cost is low, is easy to control.
Accompanying drawing explanation
Fig. 1 is the chemical reaction process of cadmium ion surface imprint sorbing material;
Fig. 2 be IIP-HQ-PHEMA/SiO2 to three heavy metal species ions in conjunction with thermoisopleth.
Detailed description of the invention
Example 1: the bond densities being 40 g/100 g, HQ by the grafting degree of the function grafting particulate HQ-PHEMA/SiO2(PHEMA of 0.1 g is 1.85mmol/g) be placed in the Cd that 500 mL concentration are 0.01 mol/L
2+ in deionized water solution, regulate the pH value of solution system with diluted sodium hydroxide solution, make pH=5.5, mixed liquor is placed in constant temperature oscillator, constant temperature oscillation 4 h, make function grafting particulate HQ-PHEMA/SiO
2to Cd
2+the absorption of ion reaches capacity, filtering particles, vacuum drying.By 0.5 g saturated adsorption Cd
2+the function grafting particulate of ion is placed in containing Cd
2+in the water of ion (concentration is 0.01mol/L) and alcohol mixed solvent (volume ratio of water and ethanol is 7:3), by the pH value of rare NaOH solution regulation system, make pH=5.5, add the dichloroether aqueous solution (1%) of 5 mL, stir at 45 DEG C and make the reaction of crosslinked trace carry out 24 h.After reaction terminates, use 0.1 molL
-1 hydrochloric acid solution cyclic washing product particles, to remove template ion Cd
2+ ion, vacuum drying, obtains Cd
2+ ion surface imprinted material IIP-HQP/SiO
2 .
Example 2: by the function grafting particulate HQ-PHEMA/SiO of 0.1 g
2 (the grafting degree of PHEMA is the bond densities of 30 g/100 g, HQ is 1.75mmol/g) be placed in the Cd that 500 mL concentration are 0.01 mol/L
2+in deionized water solution, regulate the pH value of solution system with diluted sodium hydroxide solution, make pH=5.5, mixed liquor is placed in constant temperature oscillator, constant temperature oscillation 4 h, make function grafting particulate HQ-PHEMA/SiO
2 to Cd
2+ the absorption of ion reaches capacity, filtering particles, vacuum drying.By 0.5 g saturated adsorption Cd
2+ the function grafting particulate of ion is placed in containing Cd
2+ in the water of ion (concentration is 0.01mol/L) and alcohol mixed solvent (volume ratio of water and ethanol is 7:3), by the pH value of rare NaOH solution regulation system, make pH=5, add the dichloroether aqueous solution (1%) of 4 mL, stir at 40 DEG C and make the reaction of crosslinked trace carry out 20 h.After reaction terminates, use 0.1 molL
-1hydrochloric acid solution cyclic washing product particles, to remove template ion Cd
2+ion, vacuum drying, obtains Cd
2+ion surface imprinted material IIP-HQP/SiO
2.
Example 3: by the function grafting particulate HQ-PHEMA/SiO of 0.1 g
2 (the grafting degree of PHEMA is the bond densities of 35 g/100 g, HQ is 1.8mmol/g) be placed in the Cd that 500 mL concentration are 0.01 mol/L
2+ in deionized water solution, regulate the pH value of solution system with diluted sodium hydroxide solution, make pH=5.5, mixed liquor is placed in constant temperature oscillator, constant temperature oscillation 4 h, make function grafting particulate HQ-PHEMA/SiO
2 to Cd
2+ the absorption of ion reaches capacity, filtering particles, vacuum drying.By 0.5 g saturated adsorption Cd
2+the functional particles of ion is placed in containing Cd
2+in the water of ion (concentration is 0.01mol/L) and alcohol mixed solvent (volume of water and ethanol is 7:3), by the pH value of rare NaOH solution regulation system, make pH=4.5, add the dichloroether aqueous solution (1%) of 6 mL, stir at 50 DEG C and make the reaction of crosslinked trace carry out 26 h.After reaction terminates, use 0.1 molL
-1hydrochloric acid solution cyclic washing product particles, to remove template ion Cd
2+ion, vacuum drying, obtains Cd
2+ion surface imprinted material IIP-HQP/SiO
2.
Adsorption test
Embodiment 4: static method: under the steady temperature of 25 DEG C, by the Cd that 20mL concentration series changes
2+ solion is placed in some tool plug conical flasks respectively, adjusts pH=5, adds the imprinted material IIP-HQP/SiO of the 0.05g of precise
2 , vibrate 4h in constant temperature oscillator, makes combination reach balance, adopts Cd in EDTA complexometric titration supernatant
2+ the equilibrium concentration of ion, calculates IIP-HQP/SiO
2to Cd
2+the junction at equilibrium resultant of ion is 0.44mmol/g, and uses the same method in conjunction with Cu
2+and Pb
2+junction at equilibrium resultant is only 0.02mmol/g(and sees accompanying drawing 1 trace particulate IIP-HQP/SiO
2to three heavy metal species ions in conjunction with thermoisopleth).As can be seen from Figure 1 cadmium ion surface imprint sorbing material has selective with the good binding affinity of specific recognition to cadmium sorption.
Embodiment 5: dynamic method: by the trace particulate IIP-HQP/SiO of 1.5 g
2 be contained in glass tube that internal diameter is 10 mm, make the bed volume of packed column (Bed Volume, BV) be 2 mL.Concentration is made to be the Cd of 0.01 mol/L
2+ solion (pH=5) by packed column, with the interval collection efflux of 2 BV, measures Cd in efflux with the flow velocity adverse current of 4 BV/h
2+ the concentration of ion, draws the dynamic bind curve of imprinted material, and utilizes concentration and the bed volume number of efflux, calculates IIP-HQP/SiO
2 to Cd
2+ the leakage binding capacity of ion and saturated binding capacity.Adopt same method, measure respectively and draw imprinted material IIP-HQP/SiO
2 to Cu
2+ and Pb
2+ the dynamic bind curve of ion.Result shows, Cd
2+ the leakage volume of solion is higher, is 30 BV, Cu
2+ and Pb
2+-the leakage volume of solion is only 1 BV; Cd
2+the leakage adsorbance of ion and saturated extent of adsorption are 0.32 mmol/g and 0.45 mmol/g; And Cu
2+ and Pb
2+-the leakage adsorbance of ion is almost nil, saturated extent of adsorption the former be only 0.025mmol/g, the latter is only 0.007mmol/g.Show Cd
2+ ion surface imprinted material IIP-HQP/SiO
2special identification selection and excellent binding affinity.
Embodiment 6: competitive adsorption: prepare Cd respectively
2+/ Cu
2+ with Cd
2+/ Pb
2+two kinds of binary ion mixed solution (pH value of solution is all adjusted to 5), use imprinted material IIP-HQP/SiO
2, carried out competitive Adsorption experiment.Relative to Cu
2+ ion, imprinted material is to Cd
2+the selectivity factor of ion is very high, is 25.52, shows Cd
2+ion has special identification selection; Relative to Pb
2+ion, imprinted material is to Cd
2+the selectivity factor of ion is also very high, for 22.91. clearly reveals further, and Cd
2+ion surface imprinted material IIP-HQP/SiO
2to Cd
2+ion has the special recognition capability in conjunction with selective, excellent binding affinity and superelevation really.
Embodiment 7: desorption performance: with concentration be the hydrochloric acid solution of 0.1 mol/L as eluent, upstream by saturated in conjunction with Cd
2+ the imprinted material IIP-HQ-PHEMA/SiO of ion
2packed column, carries out dynamic desorption experiment, and obtain desorption efficiency in 17 bed volumes and reach 97.75%, in 23 bed volumes, desorption efficiency can reach 99.52%.Show to be bonded to imprinted material IIP-HQ-PHEMA/SiO
2on Cd
2+ ion, can, by promptly wash-out, make adsorption column be regenerated soon, be convenient to recirculation and use.
Claims (1)
1. a preparation method for cadmium ion surface imprint sorbing material, is characterized in that: prepare as follows:
Step one, saturated adsorption: by function grafting particulate HQ-PHEMA/SiO
2 be placed in the Cd that concentration is 0.01 mol/L
2+deionized water solution, the pH value regulating solution system with sodium hydroxide solution is 5.5, is placed in constant temperature oscillator, constant temperature oscillation, filtering particles, vacuum drying, obtains saturated adsorption Cd
2+the function grafting particulate of ion; Described function grafting particulate HQ-PHEMA/SiO
2in the Cd of PHEMA grafting degree to be the bond densities of 30%-40%, HQ be 1.75mmol/g-1.85mmol/g, every 5L
2+the function grafting particulate HQ-PHEMA/SiO of 1g is put in deionized water solution
2 , the described constant temperature oscillation time is 4 h;
Step 2, crosslinked trace: saturated adsorption Cd prepared by step one
2+the function grafting particulate of ion is placed in containing Cd
2+in the water of ion and alcohol mixed solvent, the volume ratio of described water and alcohol mixed solvent water and ethanol when preparing is 7:3, by the pH value of sodium hydroxide solution regulation system to 4.5-5.5, take dichloroether as crosslinking agent, under temperature is 40 DEG C of-50 DEG C of conditions, the chlorine groups at dichloroether molecule two ends and function grafting particulate HQ-PHEMA/SiO
2quaternized between quinoline atom N on side chain carries out reaction 20-26 h, forms crosslinked trace;
Step 3, template removal: use 0.1 molL
-1hydrochloric acid solution cyclic washing step 2 product, to remove template ion Cd
2+ion, vacuum drying, leaves a large amount of Cd in the polymer foil of function grafting particulate
2+ion blotting hole, thus form Cd
2+ion surface imprinted sorbing material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210486758.1A CN102989429B (en) | 2012-11-27 | 2012-11-27 | Preparation method of cadmium ion surface imprint adsorbing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210486758.1A CN102989429B (en) | 2012-11-27 | 2012-11-27 | Preparation method of cadmium ion surface imprint adsorbing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102989429A CN102989429A (en) | 2013-03-27 |
| CN102989429B true CN102989429B (en) | 2015-05-20 |
Family
ID=47918835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210486758.1A Expired - Fee Related CN102989429B (en) | 2012-11-27 | 2012-11-27 | Preparation method of cadmium ion surface imprint adsorbing material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102989429B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804571B (en) * | 2013-08-26 | 2016-08-31 | 中国科学院城市环境研究所 | A kind of hud typed temperature and pH Lazer property metal ion trace nanogel and preparation method thereof |
| CN105669918B (en) * | 2016-02-25 | 2018-07-27 | 中北大学 | It is a kind of using methacrylic acid as the preparation method of the surface imprinted microballoon of the trypsase of monomer |
| CN105693951B (en) * | 2016-02-25 | 2018-02-09 | 中北大学 | A kind of preparation method using sodium p styrene sulfonate as the trypsase trace microballoon of monomer |
| CN106582569A (en) * | 2016-12-05 | 2017-04-26 | 北京科技大学 | Ion imprinted impregnating resin and preparation method thereof |
| CN111514861B (en) * | 2020-05-13 | 2022-07-05 | 天津工业大学 | Preparation method and application of tridentate ligand heavy metal ion imprinting material |
| CN113952940B (en) * | 2021-10-11 | 2023-11-14 | 江苏嘉通能源有限公司 | Preparation method of surface imprinting microsphere adsorption material for selectively removing Sb ions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928404A (en) * | 2010-07-09 | 2010-12-29 | 广东海洋大学 | Preparation of imprinted crosslinked chitosan resin and application thereof in removal of cadmium from pinctada martensii homogenate |
| CN102773082A (en) * | 2012-07-17 | 2012-11-14 | 中北大学 | Novel immobilized 8-hydroxyquinoline type chelate adsorption material and preparation method thereof |
-
2012
- 2012-11-27 CN CN201210486758.1A patent/CN102989429B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928404A (en) * | 2010-07-09 | 2010-12-29 | 广东海洋大学 | Preparation of imprinted crosslinked chitosan resin and application thereof in removal of cadmium from pinctada martensii homogenate |
| CN102773082A (en) * | 2012-07-17 | 2012-11-14 | 中北大学 | Novel immobilized 8-hydroxyquinoline type chelate adsorption material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Novel surface ionic imprinting materials prepared via couple grafting of polymer and ionic imprinting on surfaces of silica gel particles;Baojiao Gao et al.;《Polymer》;20070104;第48卷;第2288-2297页 * |
| 采用新型分子表面印迹技术构建手性空穴实现对氨基酸对映体识别拆分的研究;陈迎鑫等;《化学学报》;20111231;第69卷(第14期);第1705-1714页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102989429A (en) | 2013-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102989429B (en) | Preparation method of cadmium ion surface imprint adsorbing material | |
| Jiang et al. | Preparation of a novel bio-adsorbent of sodium alginate grafted polyacrylamide/graphene oxide hydrogel for the adsorption of heavy metal ion | |
| Awual | A facile composite material for enhanced cadmium (II) ion capturing from wastewater | |
| Karimi et al. | Column study of Cr (VI) adsorption onto modified silica–polyacrylamide microspheres composite | |
| CN106799215B (en) | A kind of porous spherical crosslinked resin-graphene oxide composite adsorption material and its preparation and application | |
| Gatabi et al. | Facile and efficient removal of Pb (II) from aqueous solution by chitosan-lead ion imprinted polymer network | |
| Shubha et al. | Immobilization of heavy metals from aqueous solutions using polyacrylamide grafted hydrous tin (IV) oxide gel having carboxylate functional groups | |
| CN101298040B (en) | Mercapto-functionalized polyvinyl alcohol-gelatine composite crosslinked microsphere adsorbing agent and preparation thereof | |
| CN108273477B (en) | Porous polyion liquid adsorbent and application thereof | |
| CN102188957A (en) | Polyethyleneimine modified magnetic porous adsorbent and preparation method and application thereof | |
| CN105214617A (en) | Surface imprinted chitosan microball of high efficiency selected heavy metal ion and preparation method thereof | |
| CN108031439B (en) | Magnetic solid chelating adsorption material and preparation method thereof | |
| CN102614850B (en) | Method for preparing crosslinked chitosan microsphere heavy metal ion adsorbent | |
| An et al. | Design and application of thiourea modified D301 resin for the effective removal of toxic heavy metal ions | |
| CN103910402A (en) | Granular Schwertmannite and its preparation method and use | |
| CN110115982A (en) | A kind of Beta-cyclodextrin-based chelating decolorizing and absorbing material of magnetism and preparation method thereof | |
| CN108970577A (en) | A kind of mesoporous carbon nanosheet of Co/N codope and preparation method and application | |
| CN107200375A (en) | A kind of efficient method for removing metal copper ion in waste water | |
| He et al. | Encapsulating nanosilica into polyacrylic acid and chitosan interpenetrating network hydrogel for preconcentration of uranium from aqueous solutions | |
| Liu et al. | Fabrication of sponge biomass adsorbent through UV-induced surface-initiated polymerization for the adsorption of Ce (III) from wastewater | |
| CN102225989B (en) | Preparation method of new material for separating chiral aspartic acid | |
| Kamel | Preparation and characterization of innovative selective imprinted polymer for the removal of hazardous mercury compounds from aqueous solution | |
| CN105148851B (en) | A kind of Preparation method and use of urea groups functionalization cadmium ion surface imprint adsorbent | |
| CN108568288B (en) | Application of sulfhydrylation metal organic framework UIO-66@ mSi-SH material | |
| CN104587969B (en) | Copper ion is had the preparation method of the carbon back adsorbing material of selective absorption |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Men Jiying Inventor after: Wang Ruixin Inventor after: Gao Baojiao Inventor after: Li Yanbin Inventor after: Lei Qingjuan Inventor before: Gao Baojiao Inventor before: Men Jiying Inventor before: Wang Ruixin Inventor before: Li Yanbin Inventor before: Lei Qingjuan |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: GAO BAOJIAO MEN JIYING WANG RUIXIN LI YANBIN LEI QINGJUAN TO: MEN JIYING WANG RUIXIN GAO BAOJIAO LI YANBIN LEI QINGJUAN |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150520 Termination date: 20151127 |