CN103071465B - Preparation method of spherical polymerized micron-size flyash particles - Google Patents
Preparation method of spherical polymerized micron-size flyash particles Download PDFInfo
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- CN103071465B CN103071465B CN201310012430.0A CN201310012430A CN103071465B CN 103071465 B CN103071465 B CN 103071465B CN 201310012430 A CN201310012430 A CN 201310012430A CN 103071465 B CN103071465 B CN 103071465B
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- 239000010881 fly ash Substances 0.000 title claims abstract description 95
- 239000002245 particle Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 33
- 239000000376 reactant Substances 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000012545 processing Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 239000010883 coal ash Substances 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000010183 spectrum analysis Methods 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- -1 siloxanes ethyl orthosilicate Chemical class 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
Abstract
The invention provides a preparation method of spherical polymerized micron-size flyash particles. The method is characterized by comprising the following steps: evenly grinding the flyash particles to prepare flyash powder; adding TEOS (tetraethoxysilane) and (gamma-aminopropyl) triethoxysilane respectively into the flyash powder, and stirring evenly; and adding absolute ethyl alcohol, redistilled water and concentrated sulfuric acid into the prepared solution, stirring evenly, then maintaining at a certain temperature and heating continuously; and then adding NaOH powder, holding the temperature unchanged, pouring out a reaction liquid after the reaction is finished, and washing the precipitate with acetone and the redistilled water alternately. The method takes the flyash as the main raw material, has the advantages of low cost, facilitation of operation, mild reaction conditions, capability of regulating particle sizes effectively, and the like, and has more excellent adsorbability for metal ions. Additionally, the spherical polymerized micron-size flyash particles prepared with the method can be recycled after alkali treatment, and has a potential application prospect in absorption and catalytic fields.
Description
Technical field
The invention belongs to field of material technology, be specifically related to carry out by flyash particle and Small molecular silicone T EOS and silane coupler (γ-aminopropyl) triethoxysilane the method that micron-size spherical flyash polymer particles is prepared in copolymerization.
Background technology
The solid waste that flyash is discharged as Hazards in Power Plant, main component is SiO
2, Al
2o
3, CaO, Fe
2o
3deng.Along with the development of power industry, the flyash discharge capacity of coal-burning power plant increases year by year.A large amount of flyash not only pollutes environment, and causes the wasting of resources.In order to solve this difficult problem, countries in the world have carried out research fly ash being utilized to aspect one after another.At present, flyash is mainly used in construction material, agricultural fertilizer, soil conditioner and sorbing material etc.Wherein, having loose structure and comparatively bigger serface, have stronger adsorption capacity based on flyash particulate, is that to prepare Cheap highly effective adsorbent be one of the most feasible approach of flyash high added value recycling to raw material with flyash.But due to the difference of ature of coal and the difference of burning condition, flyash is made up of the particulate with different structure and form, and the particle diameter of single powder coal ash particle is less, average grain diameter about tens microns, is unfavorable for that dress post runs and is separated, often causes secondary pollution.Therefore, the key point that forming processes is fly ash absorbent industrialized utilization is carried out to flyash.
Summary of the invention
Technical problem to be solved by this invention be to provide a kind of easy and simple to handle, the reaction time is short, react the preparation method of the micron-size spherical flyash polymer particles carried out at normal temperatures.
Solve the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of preparation method of micron-size spherical flyash polymer particles, is characterized in that comprising the steps:
(1) by fly ash grain grinding evenly, flyash powder is obtained for subsequent use;
(2) in the flyash powder of step one preparation, add ethyl orthosilicate and (γ-aminopropyl) triethoxysilane respectively, stir;
(3) add absolute ethyl alcohol in the solution configured in step 2, stir, then add redistilled water and the concentrated sulfuric acid respectively, continue to stir, then keep uniform temperature continuous heating 1.5 ~ 2.5 hours;
(4) NaOH powder is added in the solution prepared in step 3, what keep in step 3 is temperature-resistant, continue reaction 3.5 ~ 4.5 hours, reacted hypsokinesis and gone out reactant liquor, sediment acetone and redistilled water obtain micron-size spherical flyash polymer particles after replacing washing 3 ~ 4 times.
In described step 2, the mass ratio of flyash powder, ethyl orthosilicate and (γ-aminopropyl) triethoxysilane is 5:1:1 ~ 5:3:1.
In described step 3, the mass ratio of absolute ethyl alcohol, redistilled water and the concentrated sulfuric acid is 20:1:1 ~ 20:1:3.
In flyash powder in described step 2 and step 4, the mass ratio of NaOH powder is 1:0.2 ~ 1:0.4.
The mass ratio of the flyash powder in described step 2 and the absolute ethyl alcohol in step 3 is 1:2.
Heating in described step 3 keeps temperature to be 55 DEG C ~ 65 DEG C.
The preparation method of micron-size spherical flyash polymer particles of the present invention, have easy and simple to handle, reaction condition is gentle, effectively can regulate the advantages such as particle size.The present invention take flyash as primary raw material, not only with low cost, and has important theory and realistic meaning to economize on resources, preserve the ecological environment, promote economic development, set up conservation-minded society and friendly environment society.
In addition, micron-size spherical flyash polymer particles prepared by the present invention has spherical appearance, inside particles is by flyash particulate and siloxanes ethyl orthosilicate and silane coupler (γ-aminopropyl) triethoxysilane copolymerization, formation take silica as the 3 D pore canal of skeleton, flyash doping, due to the existence of amino, it has more excellent adsorptivity for metal ion.In addition, with after alkali treatment after micron-size spherical flyash polymer particles prepared by the present invention uses, reusable edible, has potential application prospect in absorption and catalytic field.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the micron-size spherical flyash polymer particles of preparation.
Fig. 2 is the partial enlarged drawing of the micron-size spherical flyash polymer particles in Fig. 1.
Fig. 3 is the energy spectrum analysis spectrogram of the micron-size spherical flyash polymer particles of preparation.
Fig. 4 is the infrared spectrum of the micron-size spherical flyash polymer particles of preparation.
Fig. 5 is the thermogravimetric analysis spectrogram of the micron-size spherical flyash polymer particles of preparation.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in more detail, but the invention is not restricted to these embodiments.
Embodiment 1:
A preparation method for micron-size spherical flyash polymer particles, is characterized in that comprising the steps:
(1) by fly ash grain grinding evenly, flyash powder is obtained for subsequent use;
(2) in the flyash powder of step one preparation, ethyl orthosilicate and (γ-aminopropyl) triethoxysilane is added respectively, the mass ratio of flyash powder, ethyl orthosilicate and (γ-aminopropyl) triethoxysilane is 5:2:1, stirs;
(3) absolute ethyl alcohol is added in the solution configured in step 2, stir, then redistilled water and the concentrated sulfuric acid is added respectively, the mass ratio of absolute ethyl alcohol, redistilled water and the concentrated sulfuric acid is 20:1:2, the mass ratio of the flyash powder added in absolute ethyl alcohol and step 2 is 1:2, continue to stir, continuous heating 2 hours at then maintaining the temperature at 60 DEG C;
(4) NaOH powder is added in the solution prepared in step 3, the mass ratio adding the flyash powder in NaOH powder and step 2 is 1:0.3, what keep in step 3 is temperature-resistant, continue reaction 4 hours, reacted hypsokinesis and gone out reactant liquor, sediment acetone and redistilled water obtain micron-size spherical flyash polymer particles after replacing washing 3 ~ 4 times.
Embodiment 2:
In the processing step two of the present embodiment, the mass ratio of flyash powder, ethyl orthosilicate, (γ-aminopropyl) triethoxysilane is 5:1:1, and other processing step is identical with embodiment 1.
Embodiment 3:
In the processing step two of the present embodiment, the mass ratio of flyash powder, ethyl orthosilicate, (γ-aminopropyl) triethoxysilane is 5:3:1, and other processing step is identical with embodiment 1.
Embodiment 4:
In the processing step three of the present embodiment, the mass ratio of absolute ethyl alcohol, redistilled water and the concentrated sulfuric acid is 20:1:1, and other processing step is identical with embodiment 1.
Embodiment 5:
In the processing step three of the present embodiment, the mass ratio of absolute ethyl alcohol, redistilled water and the concentrated sulfuric acid is 20:1:3, and other processing step is identical with embodiment 1.
Embodiment 6:
In the processing step three of the present embodiment, continuous heating 2.5 hours at maintaining the temperature at 55 DEG C, other processing step is identical with embodiment 1.
Embodiment 7:
In the processing step three of the present embodiment, continuous heating 1.5 hours at maintaining the temperature at 65 DEG C, other processing step is identical with embodiment 1.
Embodiment 8:
In the processing step four of the present embodiment, the mass ratio of the flyash powder in NaOH powder and step 2 is 1:0.2, and other processing step is identical with embodiment 1.
Embodiment 9:
In the processing step four of the present embodiment, the mass ratio of the flyash powder in NaOH powder and step 2 is 1:0.4, and other processing step is identical with embodiment 1.
In order to determine optimised process step of the present invention, carried out a large amount of laboratory research tests, various test situation is as follows:
(1) selection of coupling agent
Use KH550 respectively, KH560, KH570 make coupling agent, copolymerization in ethanolic solution, generate spherical powder coal ash particle in the identical lower reaction respectively of other condition.Result of the test shows: make coupling agent with KH550, product flyash particle dispersion degree and spherical morphology best.
(2) pulp furnish is on the impact of flyash polymer particles pattern
In step 2, select flyash powder, ethyl orthosilicate and (γ-aminopropyl) triethoxysilane mass ratio to be 5:2:1,5:1:1,5:3:1 respectively, be prepared into micron-size spherical flyash particle.Finally observe by SEM respectively prepared micron-size spherical flyash particle, the micron-size spherical flyash particle spherical morphology prepared when finding that flyash powder, ethyl orthosilicate and (γ-aminopropyl) triethoxysilane mass ratio are 5:2:1 is best.
(3) concentrated sulfuric acid consumption is on the impact of flyash polymer particles pattern
In step 3, the mass ratio selecting absolute ethyl alcohol, redistilled water and the concentrated sulfuric acid is respectively 20:1:1,20:1:2,20:1:3, is prepared into micron-size spherical flyash particle.Prepared micron-size spherical flyash particle SEM is observed, and the micron-size spherical flyash particle dispersion degree prepared when the mass ratio of discovery absolute ethyl alcohol, redistilled water and the concentrated sulfuric acid is 20:1:2 is best, and spherical morphology is best.As shown in Figures 1 and 2, the electron scanning micrograph of to be concentrated sulfuric acid consumption the be electron scanning micrograph of micron-size spherical flyash particle that 2mL obtains and the surperficial partial enlargement of correspondence.
(4) NaOH consumption is on the impact of flyash polymer particles pattern
In step 4, the mass ratio of the flyash powder selected in NaOH powder and step 2 is respectively 1:0.2,1:0.3,1:0.4, is prepared into micron-size spherical flyash particle.Prepared micron-size spherical flyash particle SEM is observed, and the micron-size spherical flyash particle dispersion degree prepared when finding that NaOH powder is 1:0.3 with the mass ratio of the flyash powder in step 2 is best, spherical morphology the best.
As shown in Figure 1, Figure 2, for flyash powder, ethyl orthosilicate and (γ-aminopropyl) triethoxysilane solution quality in step 2 than for 5:2:1, in step 3 the mass ratio of absolute ethyl alcohol, redistilled water and the concentrated sulfuric acid be 20:1:2 and in step 4, NaOH powder is 1:0.3 with the mass ratio of the flyash powder in step 2 time the electron scanning micrograph of micron-size spherical flyash particle that obtains and the electron scanning micrograph of corresponding surperficial partial enlargement.
In order to verify beneficial effect of the present invention, the micron-size spherical coal ash polymer particles that inventor adopts the embodiment of the present invention 1 to prepare, use SEM, Fourier transformation infrared spectrometer, thermogravimetric analyzer to carry out observation experiment respectively, various test situation is as follows:
Observe article: micron-size spherical flyash polymer particles.
Laboratory apparatus: SEM, model is XL-20, and produced by Philips company of Britain, Electronic Speculum self is with energy spectrum analysis software to carry out energy spectrum analysis; Fourier transformation infrared spectrometer, model is that AVTAR360 is produced by Nicolet company; Thermogravimetric analyzer, model is PEVKIN-ELMER, is produced by TA company of the U.S..
(1) observe
By the method for testing of SEM, micron-size spherical coal ash polymer particles is observed.
(2) test
By the method for testing of power spectrum, Fourier transformation infrared spectrometer, thermogravimetric analyzer, micron-size spherical coal ash polymer particles is tested.
(3) observed result
As shown in Figure 3, as shown in Figure 4, thermal gravimetric analysis curve as shown in Figure 5 for FFIR curve in the energy spectrum analysis of micron-size spherical flyash polymer particles.
From Fig. 1, Fig. 2, micron-size spherical flyash polymer particles is spherical in shape, structural integrity, and monodispersity is good, and diameter about 200 μm, surface presentation goes out graininess pattern.Fig. 3 is the energy spectrum analysis of flyash polymer particles, and wherein Au element is from gold-plated film before Electronic Speculum test, and Fe, Mg, Al, S, Np and Ca element is from flyash component, and N element is from silane, C and Si then may from flyash or silane components.In the diagram, 3360,3282 cm
– 1with 1577 cm
-1what occur is absorbed as amino characteristic IR absorbance peaks; 1123 and 1037cm
-1the peak occurred should be attributed to Si-O-Si symmetric vibration absworption peak.By comparing, infrared spectrum curve shows that fly ash grain and ethyl orthosilicate and silane coupler (γ-aminopropyl) triethoxysilane there occurs copolymerization, containing to the amido functional group about the strong coordination of metal ion, can be used as catalyst or adsorbent.As seen from Figure 5, flyash polymer particles has good heat endurance, and its residual solid is metal or nonmetal oxide, mainly SiO
2, Al
2o
3, CaO, Fe
2o
3deng, residual volume is 80.3%.
Claims (6)
1. a preparation method for micron-size spherical flyash polymer particles, is characterized in that, comprises the steps:
(1) by fly ash grain grinding evenly, flyash powder is obtained for subsequent use;
(2) add ethyl orthosilicate and (γ-aminopropyl) triethoxysilane in the flyash powder prepared in step (1) respectively, stir;
(3) add absolute ethyl alcohol in the solution configured in step (2), stir, then add redistilled water and the concentrated sulfuric acid respectively, continue to stir, then keep uniform temperature continuous heating 1.5 ~ 2.5 hours;
(4) NaOH powder is added in the solution prepared in step (3), what keep in step (3) is temperature-resistant, continue reaction 3.5 ~ 4.5 hours, reacted hypsokinesis and gone out reactant liquor, sediment acetone and redistilled water obtain micron-size spherical flyash polymer particles after replacing washing 3 ~ 4 times.
2. according to the preparation method of micron-size spherical flyash polymer particles according to claim 1, it is characterized in that: in described step (2), the mass ratio of flyash powder, ethyl orthosilicate and (γ-aminopropyl) triethoxysilane is 5:1:1 ~ 5:3:1.
3. according to the preparation method of micron-size spherical flyash polymer particles according to claim 1, it is characterized in that: in described step (3), the mass ratio of absolute ethyl alcohol, redistilled water and the concentrated sulfuric acid is 20:1:1 ~ 20:1:3.
4. according to the preparation method of the micron-size spherical flyash polymer particles described in claim 1 or 2, it is characterized in that: the mass ratio of the flyash powder in described step (2) and the middle NaOH powder of step (4) is 1:0.2 ~ 1:0.4.
5. according to the preparation method of the micron-size spherical flyash polymer particles described in claim 1 or 3, it is characterized in that: the mass ratio of the absolute ethyl alcohol in the flyash powder in described step (2) and step (3) is 1:2.
6. according to the preparation method of the micron-size spherical flyash polymer particles described in claim 1 or 3, it is characterized in that: the heating-up temperature described in described step (3) remains 55 DEG C ~ 65 DEG C.
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| CN105688847B (en) * | 2016-03-11 | 2018-08-14 | 四川大学 | A kind of gelatin/flyash composite adsorbing material and preparation method thereof |
| CN106540652B (en) * | 2016-10-04 | 2018-10-26 | 青岛大学 | A kind of quaternary ammonium salt cationic is modified flying dust and preparation method thereof |
| CN106423109B (en) * | 2016-10-04 | 2018-10-26 | 青岛大学 | A kind of cation-modified flying dust adsorbent and preparation method thereof |
| CN106984278A (en) * | 2017-05-18 | 2017-07-28 | 付主枝 | A kind of processing method of low concentration weight hexavalent chromium waste water |
| CN108311124B (en) * | 2018-03-08 | 2021-02-02 | 东华理工大学 | Preparation method and application of hyperbranched polysiloxane modified fly ash |
| CN108927104A (en) * | 2018-08-02 | 2018-12-04 | 深圳市深港产学研环保工程技术股份有限公司 | A kind of preparation method protonating flyash |
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| CN101585954A (en) * | 2008-05-22 | 2009-11-25 | 中国科学院过程工程研究所 | Silicon dioxide hollow sphere/polymer composite heat insulating material and method for preparing same |
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| CN101585954A (en) * | 2008-05-22 | 2009-11-25 | 中国科学院过程工程研究所 | Silicon dioxide hollow sphere/polymer composite heat insulating material and method for preparing same |
Non-Patent Citations (1)
| Title |
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| Synthesis and characterization of novel aminopropylated fly ash catalyst and its beneficial application in base catalyzed Knoevenagel condensation reaction;Deepti Jain et al.;《Fuel Processing Technology》;20111229;第95卷;第119-126页 * |
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Owner name: TAIYUAN UNIV. OF TECHNOLOGY Free format text: FORMER OWNER: DU YALI Effective date: 20150514 Owner name: SHANXI YUNUO HUANNENG TECHNOLOGY SERVICE CO., LTD. Effective date: 20150514 |
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Inventor after: Wu Xu Inventor after: Du Yali Inventor after: Song Shaofei Inventor after: Zhao Qiang Inventor after: Zhu Baolin Inventor after: Liu Youjun Inventor before: Du Yali Inventor before: Song Shaofei Inventor before: Zhao Qiang Inventor before: Zhu Baolin Inventor before: Liu Youjun |
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