水相溶胶路线制备钇掺杂ZrO2纳滤膜及其分离性能研究

doi:10.15541/jim20150557

摘要/Abstract

摘要：

以氧氯化锆为前驱体, 采用环境友好的水相溶胶路线制备出完整无缺陷的管式钇掺杂的ZrO₂(YSZ)纳滤膜。并考察了溶胶粒径, 材料晶型与孔结构的关系。结果表明: 前驱体浓度越低, 所制备的溶胶粒径越小, 经400℃煅烧得到的粉末中单斜相含量越高, 堆积孔径增大; 向ZrOC₂O₄溶胶中添加8mol%钇, 有效抑制了ZrO₂四方相向单斜相的转变, 延缓晶粒生长, 同时防止膜层开裂。经纳滤测试表明, 实验制备的YSZ纳滤膜对PEG的截留分子量为860 Da, 纯水渗透率为200 L/(m²·h·MPa)。实验还详细考察了YSZ纳滤膜在pH=6, 压力0.8 MPa的条件下对NaCl、Na₂SO₄、CaCl₂和MgCl₂ 4种溶液的截留性能, 结果显示YSZ纳滤膜对0.005 mol/L CaCl₂和MgCl₂溶液的离子截留率分别达到65%和78%。

关键词: 氧化锆, 纳滤膜, 溶胶-凝胶, 离子截留

Abstract:

Crack-free tubular yttria-stabilized-zirconia (YSZ) nanofiltration membranes was fabricated via an aqueous Sol-Gel process, using zirconium oxychloride as precursor and water as solvent. This procedure was completely free of organic solvent and thus was environmentally friendly. The influences of precursor concentration and calcination temperature on the particle size of sols, crystal and pore structure were investigated. The results revealed that the sol prepared with lower precursor concentration and calcined at 400℃, has higher content of monoclinic phase, thus leading to the increase of pore size. Subsequently, addition of 8mol% yttrium into the sol inhibits phase transformation from tetragonal to monoclinic and grain growth, as well as avoid membrane cracking. In addition, retention experiment result shows that the YSZ nanofiltration membrane exhibits a molecular weight cut-off (MWCO) of 860 Da and a water permeability of 200 L/(m²·h·MPa). Furthermore, ions retention properties of YSZ nanofiltration membrane towards four solutions like NaCl, Na₂SO₄, CaCl₂, and MgCl₂, were conducted at pH 6 and a transmembrane pressure of 0.8 MPa. The retention properties of YSZ nanofiltration membrane towards CaCl₂ and MgCl₂ solutions reach maximum values of 65% and 78%, respectively.

Key words: ZrO2, nanofiltration membrane, Sol-Gel, ions retention

中图分类号:

TQ174

笪晓薇, 邱鸣慧, 范益群. 水相溶胶路线制备钇掺杂ZrO₂纳滤膜及其分离性能研究[J]. 无机材料学报, 2016, 31(6): 621-626.

DA Xiao-Wei, QIU Ming-Hui, FAN Yi-Qun. Fabrication and Characterization of Y-doped ZrO₂ Nanofiltration Membranes by Aqueous Sol-Gel Process[J]. Journal of Inorganic Materials, 2016, 31(6): 621-626.

图/表 10

图1 不同氧氯化锆浓度的溶胶粒径分布

Fig. 1 Particle size distribution of sols prepared with different concentrations of precursor

图2 不同前驱体浓度的溶胶经400℃煅烧得到的ZrO2粉体的XRD图谱(a)及单斜相体积分数(b)

Fig. 2 XRD patterns (a) and monoclinic phase composition (b) of ZrO2 powder prepared from sols synthesized with different concentrations of precursor and calcinated at 400℃

图3 不同前驱体浓度的溶胶经400℃煅烧获得的ZrO2粉体的吸附平衡等温线

Fig. 3 N2-adsoption isotherm of ZrO2 powder prepared from sols synthesized with different concentrations of precursor and calcinated at 400℃

表1 不同前驱体浓度的溶胶经400℃煅烧获得的ZrO2粉体的孔结构数据

Table 1 Pore structure data of ZrO2 powder prepared from sols synthesized with different concentrations of precursor and calcinated at 400℃

C/(mol·L^-1)	Adsorption type	BET	BJH
C/(mol·L^-1)	Adsorption type	Specific surface area/ (m²·g^-1)	Pore width/ nm	Pore volume/ (cm³·g^-1)
0.03	IV	30.76	4.7	0.036
0.06	IV	42.05	5.0	0.053
0.10	IV	42.15	4.9	0.052
0.20	IV	35.25	6.6	0.058

图4 不同温度煅烧获得的ZrO2 (a)及YSZ (b)粉体的XRD图谱

Fig. 4 XRD patterns of ZrO2 (a) and YSZ (b) powders calcined at different temperatures

图 5 煅烧温度对粉体的平均晶粒尺寸的影响

Fig. 5 Relation between average crystallite size of the powders and calcination temperature

图 6 400℃煅烧得到的ZrO2 (a)及YSZ (b)粉体的HRTEM照片

Fig. 6 HRTEM images of ZrO2 (a) and YSZ (b) powder calcinated at 400℃

图7 ZrO2 (a)及YSZ (b)陶瓷膜的SEM照片

Fig. 7 FESEM micrographs of ZrO2 (a) and YSZ (b) membranes

图8 纳滤膜的纯水渗透性能(a)及对PEG截留性能(b)

Fig. 8 Water flux (a) and PEG retention (b) of the nanofiltration membranes

图 9 YSZ纳滤膜对离子的截留性能随盐溶液浓度的变化

Fig. 9 Effect of concentration on ions retention properties of YSZ nanofiltration membrane

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水相溶胶路线制备钇掺杂ZrO₂纳滤膜及其分离性能研究

Fabrication and Characterization of Y-doped ZrO₂ Nanofiltration Membranes by Aqueous Sol-Gel Process

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