介孔ZrO_2及Y_2O_3稳定ZrO_2球形颗粒的准气相反应法合成与表征
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摘要
氧化锆是唯一一种同时具有表面酸性与碱性中心的材料,再加上其良好的离子交换和电荷传导等性能,从而使其成为一种理想的多功能催化剂。随着介孔氧化锆的合成及表征技术的发展,介孔氧化锆材料的应用范围也越来越广,就如,光致发光材料、催化剂及载体、药物可控释放、水处理吸附材料、色谱柱填料等。本论文采用准气相反应法进行介孔氧化锆及钇稳定介孔氧化锆的合成,并通过SEM、TEM、XRD、TG/DTA、N2吸—脱附、激光粒度仪等对颗粒各方面性能进行了测试表征。
本工作首先进行了准气相反应法装置与工艺的改进：于收集器进料管出口处增设筛孔、加粗反应器、并在反应器出口管段增设真空表、对雾化器封盖处密封并增设流量计、并对收集所得悬浮液进行陈化处理。通过以上改进后,合成反应条件及反应结果趋于稳定。
其次,再通过正交实验(L1837)确定了合成氧化锆前驱物球形颗粒的较佳工艺条件：WZrOCi2·H2O=30%、QNH3=60L/h、P真空=0.02MPa、Qair/QNH3=1、陈化3d。在此较佳条件下合成出的氧化锆前驱物颗粒为光滑的球形颗粒,平均粒径约4μm且无明显空心球存在。再由正交实验结果分析知,对实验结果影响最大的工艺条件是氯氧化锆溶液的浓度,在正交实验条件范围内,氨气流量和真空度对实验结果的影响相对较小。
通过对前驱物球形颗粒进行水热处理和室温干燥后煅烧,获得了氧化锆微粉。其中常温干燥后进行煅烧的结果较好——颗粒仍保持球形,且破碎颗粒也较少。
最后,采用合成氧化锆的较佳实验条件并进行介孔钇稳定氧化锆球形颗粒的合成,掺杂量分别为1.5mol% Y2O3 (ZrYO系列)和3mol%Y2O3 (ZrOY系列),采用干燥后煅烧的方式进行前驱物的后处理。由TG/DTA、XRD、SEM、TEM及氮气吸—脱附的表征可知,两系列的ZrO_2/Y2O_3颗粒均为球形且无明显空心现象,500-1200℃煅烧后晶相组成以四方相为主,比表面积为34.3887m2/g(600℃煅烧后)。
Zirconia is the unique material with both acidic and basic centers, coupled with its good ion-exchange and charge transfer properties. Therefore, Zirconia is an ideal multi-functional catalyst. With the advance on technologies of the preparation and characterization of mesoporous Zirconia, mesoporous Zirconia materials are increasingly applied to abroad areas, for example, photoluminescence materials, catalyst and its carrier, drug delivery, absorption materials for sewage treatment, chromatographic column packing, and so on. In this thesis, using quasi-gaseous state reaction method, mesoporous Zirconia and Yttria-stabilized Zirconia were prepared and characterized by SEM, TEM, XRD, TG/DTA, N2 gas absorption-desorption, laser particle size analyzer, and etc.
Firstly, the equipment and process for quasi-gaseous state reaction were improved, which involved making sieve-like holes on the outlet of the feed tube of collector, expanding the diameter of reactor, fixing a vacuum meter on the outlet tube of reactor, sealing the cover of atomizer and adding flow meter before the atomizer, and aging the collected suspensions in the collector. By above improvements, the synthesis reaction conditions and results are becoming stable.
Secondly, the optimal synthesis conditions for Zirconia precursor spherical particles were determined by the orthogonal experiment (L1837):WZrOCl2·H2O=30%, QNH3=60L/h, Pvacuum=0.02MPa, Qair/QNH3=1, aging for 72h. The Zirconia precursor particles synthesized using this optimal process are spherical shape with smooth surface, its average size is about 4μm, and there are scarcely hollow spheres present. Moreover, according to orthogonal experimental results, the concentration of Zirconium oxychloride solution is the main factor affecting the results, and effect of the ammonia gas flow and the system vacuum were little relatively.
Zirconia powders were obtained via hydrothermal method and calcining precursor spherical particles after dried at room temperature. And Zirconia powders obtained by calcining were better than those obtaining via hydrothermal method, in which the particles were still spherical shape and broken little.
Finally, zirconia powder were obtained via calcining spherical particles of the precursor dried at room temperature or hydrothermal method. The results, obtained via calcining spherical particles of the precursor dried at room temperature, were better than obtaining via hydrothermal method, in which the particles were still spherical, and only a few were broken.
Finally, through the above optimal preparation conditions for Zirconia, mesoporous Yttria-stabilized Zirconia spherical particles were prepared as well, marked as ZrYO series (1.5mol% Y2O3 doped) and ZrOY series (3mol% Y2O3 doped), respectively. The post-processing method for the ZrO2/Y2O3 precursor utilizes calcining the precursor spherical particles after dried at room temperature. By the characterizations of TG/DTA, XRD, SEM, TEM and nitrogen gas absorption-desorption, it can be concluded that the two series of ZrO2/Y2O3 particles are all spherical shape and hardly any hollow, whose phase compositions are major tetragonal ZrO2 after calcined at 500-1200℃, and BET surface area is around 34.3887 m2/g.
本工作首先进行了准气相反应法装置与工艺的改进：于收集器进料管出口处增设筛孔、加粗反应器、并在反应器出口管段增设真空表、对雾化器封盖处密封并增设流量计、并对收集所得悬浮液进行陈化处理。通过以上改进后,合成反应条件及反应结果趋于稳定。
其次,再通过正交实验(L1837)确定了合成氧化锆前驱物球形颗粒的较佳工艺条件：WZrOCi2·H2O=30%、QNH3=60L/h、P真空=0.02MPa、Qair/QNH3=1、陈化3d。在此较佳条件下合成出的氧化锆前驱物颗粒为光滑的球形颗粒,平均粒径约4μm且无明显空心球存在。再由正交实验结果分析知,对实验结果影响最大的工艺条件是氯氧化锆溶液的浓度,在正交实验条件范围内,氨气流量和真空度对实验结果的影响相对较小。
通过对前驱物球形颗粒进行水热处理和室温干燥后煅烧,获得了氧化锆微粉。其中常温干燥后进行煅烧的结果较好——颗粒仍保持球形,且破碎颗粒也较少。
最后,采用合成氧化锆的较佳实验条件并进行介孔钇稳定氧化锆球形颗粒的合成,掺杂量分别为1.5mol% Y2O3 (ZrYO系列)和3mol%Y2O3 (ZrOY系列),采用干燥后煅烧的方式进行前驱物的后处理。由TG/DTA、XRD、SEM、TEM及氮气吸—脱附的表征可知,两系列的ZrO_2/Y2O_3颗粒均为球形且无明显空心现象,500-1200℃煅烧后晶相组成以四方相为主,比表面积为34.3887m2/g(600℃煅烧后)。
Zirconia is the unique material with both acidic and basic centers, coupled with its good ion-exchange and charge transfer properties. Therefore, Zirconia is an ideal multi-functional catalyst. With the advance on technologies of the preparation and characterization of mesoporous Zirconia, mesoporous Zirconia materials are increasingly applied to abroad areas, for example, photoluminescence materials, catalyst and its carrier, drug delivery, absorption materials for sewage treatment, chromatographic column packing, and so on. In this thesis, using quasi-gaseous state reaction method, mesoporous Zirconia and Yttria-stabilized Zirconia were prepared and characterized by SEM, TEM, XRD, TG/DTA, N2 gas absorption-desorption, laser particle size analyzer, and etc.
Firstly, the equipment and process for quasi-gaseous state reaction were improved, which involved making sieve-like holes on the outlet of the feed tube of collector, expanding the diameter of reactor, fixing a vacuum meter on the outlet tube of reactor, sealing the cover of atomizer and adding flow meter before the atomizer, and aging the collected suspensions in the collector. By above improvements, the synthesis reaction conditions and results are becoming stable.
Secondly, the optimal synthesis conditions for Zirconia precursor spherical particles were determined by the orthogonal experiment (L1837):WZrOCl2·H2O=30%, QNH3=60L/h, Pvacuum=0.02MPa, Qair/QNH3=1, aging for 72h. The Zirconia precursor particles synthesized using this optimal process are spherical shape with smooth surface, its average size is about 4μm, and there are scarcely hollow spheres present. Moreover, according to orthogonal experimental results, the concentration of Zirconium oxychloride solution is the main factor affecting the results, and effect of the ammonia gas flow and the system vacuum were little relatively.
Zirconia powders were obtained via hydrothermal method and calcining precursor spherical particles after dried at room temperature. And Zirconia powders obtained by calcining were better than those obtaining via hydrothermal method, in which the particles were still spherical shape and broken little.
Finally, zirconia powder were obtained via calcining spherical particles of the precursor dried at room temperature or hydrothermal method. The results, obtained via calcining spherical particles of the precursor dried at room temperature, were better than obtaining via hydrothermal method, in which the particles were still spherical, and only a few were broken.
Finally, through the above optimal preparation conditions for Zirconia, mesoporous Yttria-stabilized Zirconia spherical particles were prepared as well, marked as ZrYO series (1.5mol% Y2O3 doped) and ZrOY series (3mol% Y2O3 doped), respectively. The post-processing method for the ZrO2/Y2O3 precursor utilizes calcining the precursor spherical particles after dried at room temperature. By the characterizations of TG/DTA, XRD, SEM, TEM and nitrogen gas absorption-desorption, it can be concluded that the two series of ZrO2/Y2O3 particles are all spherical shape and hardly any hollow, whose phase compositions are major tetragonal ZrO2 after calcined at 500-1200℃, and BET surface area is around 34.3887 m2/g.
引文
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[2]Beck, J. S.; Vartuli, J. C.; Roth, W. J.; et al. A new family of mesoporous molecular sieves prepared with liquid crystal templates. J. Am. Chem. Soc.,1992,114(27), pp 10834-10843.
[3]Huo, Q.; Margolese, D. I.; Feng, P.; et al. Generalized Syntheses of Periodic Surfactant/Inorganic Composite Materials. Nature,1994,368(6469), PP 317-321.
[4]Zhao, W.; Gu, J. L.; Zhang, L. X.; et al. Fabrication of Uniform Magnetic Nanocomposite Spheres with a Magnetic Core/Mesoporous Silica Shell Structure. J. Am. Chem. Soc.,2005,127(25), PP 8916-8917.
[5]Guan, M.; Liu, W.; Shao, Y. L.; et al. Preparation, characterization and adsorption properties studies of 3-(methacryloyloxy)propyltrimethoxysilane modified and polymerized sol-gel mesoporous SBA-15 silica molecular sieves. Microporous Mesoporous Mater.2009,123, PP 193-201
[6]任瑜,钱林平,岳斌,贺鹤勇.对环氧化反应具有高催化活性的钛硅介孔分子筛的合成.催化学报,2003,24(12),PP 947-950.
[7]张辉,刘莲云,安振涛,张登君,唐清.ZrO2球的准气相反应合成.化学学报,2005,63(12),PP 1131-1135.
[8]Liu, X. M.; Lu, G. Q.; Yan, Z. F. Synthesis and Stabilization of Nanocrystalline Zirconia with MSU Mesostructure. J. Phys. Chem. B,2004,108(40), PP 15523-15528.
[9]Mamak, M.; Coombs, N.; Ozin, G. Self-Assembling Solid Oxide Fuel Cell Materials: Mesoporous Yttria-Zirconia and Metal-Yttria-Zirconia Solid Solutions. J. Am. Chem. Soc.,2000,122(37), PP 8932-8939.
[10]Verweij, H. Nanocrystalline and Nanoporous Ceramics. Adv. Mater.1998,10(17), PP 1483-1486.
[11]Chen, H. R.; Shi, J. L.; Hua, L. Z.; Ruan, M. L.; Yan, D. S. Mater. Parameter control in the synthesis of ordered porous zirconium oxide. Lett.,2001,51, PP 187-193.
[12]Za'rate, J.; Jua'rez, H.; Contreras, M. E.; Pe'rez, R. Experimental design and results from the preparation of precursory powders of ZrO2(3%Y2O3)/(10-95)%Al2O3 composite. Powder Technol.,2005,159, PP 135-141.
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