沸石分子筛/微米氧化锆复合颗粒的制备与性能
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摘要
为解决东北地区地下水低温高氟问题,采用试验室自制的沸石分子筛/微米氧化锆(简称Z-MZ)复合吸附颗粒去除水中F-,通过优化工艺条件确定其最佳制备方法,并利用扫描电镜(SEM)、能谱分析(EDS)、比表面积(BET)、傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)分析表面物化特性。结果表明,Z-MZ最佳制备条件为:盐酸质量分数8%,微米氧化锆与沸石分子筛的质量比为0.8∶1,制备温度10℃,制备时间10 h。制得的Z-MZ对F-吸附量达到0.35 mg/g,去除率达到93.99%。通过SEM可观察到Z-MZ表面有较多凸起,比表面积为24.606 m2/g,FTIR结果表明,微米氧化锆的特征官能团Zr-O、Zr-OH已存在于该复合颗粒中;XRD分析表明,沸石分子筛在嵌入微米氧化锆微粒后其晶相发生了改变。
In order to solve the problem of low temperature and high fluorine in groundwater in northeast China, laboratory-made zeolite molecular sieve/micron zirconia(hereinafter referred to as Z-MZ) composite adsorption particles were used to remove F-in water, and the optimal preparation method was determined by optimizing the process conditions, and scanning was carried out. Electron microscopy(SEM), energy spectrum analysis(EDS), specific surface area(BET), Fourier transform infrared spectroscopy(FTIR), and X-ray diffraction(XRD) were used to analyze surface physicochemical properties. The results showed that the optimal preparation conditions of Z-MZ were: 8% hydrochloric acid concentration, the mass ratio of micron zirconia to zeolite molecular sieve was 0.8∶1, the preparation temperature was 10 ℃, and the preparation time was 10 h. The obtained Z-MZ had an F-adsorption amount of 0.35 mg/g and a removal rate of 93.99%. It can be observed by SEM that there are many protrusions on the surface of Z-MZ, and the specific surface area is 24.606 m2/g. The FTIR results indicate that the characteristic functional groups Zr-O and Zr-OH of micron zirconia are already present in the composite particles, and XRD indicates zeolite. The molecular sieve changes its crystal phase after embedding the micron zirconia particles.
In order to solve the problem of low temperature and high fluorine in groundwater in northeast China, laboratory-made zeolite molecular sieve/micron zirconia(hereinafter referred to as Z-MZ) composite adsorption particles were used to remove F-in water, and the optimal preparation method was determined by optimizing the process conditions, and scanning was carried out. Electron microscopy(SEM), energy spectrum analysis(EDS), specific surface area(BET), Fourier transform infrared spectroscopy(FTIR), and X-ray diffraction(XRD) were used to analyze surface physicochemical properties. The results showed that the optimal preparation conditions of Z-MZ were: 8% hydrochloric acid concentration, the mass ratio of micron zirconia to zeolite molecular sieve was 0.8∶1, the preparation temperature was 10 ℃, and the preparation time was 10 h. The obtained Z-MZ had an F-adsorption amount of 0.35 mg/g and a removal rate of 93.99%. It can be observed by SEM that there are many protrusions on the surface of Z-MZ, and the specific surface area is 24.606 m2/g. The FTIR results indicate that the characteristic functional groups Zr-O and Zr-OH of micron zirconia are already present in the composite particles, and XRD indicates zeolite. The molecular sieve changes its crystal phase after embedding the micron zirconia particles.
引文
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[3]邓建国,赵金芳.含高氟工业废水去除氟的技术探讨[J].世界有色金属,2018(7):230-232.
[4]ZHAO Z W,GENG C,YANG C,et al.A novel flake-ball-like magnetic Fe3O4/γ-Mn O2 meso-porous nano-composite:Adsorption of fluorinion and effect of water chemistry[J].Chemosphere,2018,209:173-181.
[5]TIAN Z L,GUO W C,ZHANG Z J,et al.Removal of fluorine ions from industrial zinc sulfate solution by a layered aluminum-based composite[J].Hydrometallurgy,2017,171:222-227.
[6]赵凌波,夏传,吴班.石灰沉淀-电凝聚法处理高含氟酸性废水工程设计[J].硫酸工业,2017(10):32-33,37.
[7]邹维,杨大锦,刘俊场,等.硫酸锌溶液离子交换脱氟氯[J].有色金属(冶炼部分),2018(7):5-8.
[8]朱帅,贾静,饶竹.吹扫捕集/气相色谱-质谱法测定水中痕量全氟碘烷类化合物[J].分析测试学报,2018(11):1359-1364.
[9]王春蓉.沸石分子筛的性能与应用研究[J].化学与粘合,2010,32(4):76-78.
[10]BUSCA G.Zeolites and other structurally microporous solids as acidbase materials[J].Heterogeneous Catalytic Materials,2014(7):197-249.
[11]HUO Q S.Synthetic chemistry of the inorganic ordered porous materials[J].Modern Inorganic Synthetic Chemistry,2011(16):339-373.
[12]武卫东,王闯,孟晓伟,等.含添加剂沸石分子筛混合吸附剂物理特性及其制冷应用性能[J].化工进展,2016,35(3):692-699.
[13]SAMATYA S,YüKSELü,YüKSEL M,et al,Removal of fluoride from water bymetal ions(Al3+,La3+and ZrO2+)loaded natural zeolite[J].Technol,2007,42:2033-2047.
[14]LIU H,DENG S,LI Z J,et al.Preparation of Al-Ce hybrid adsorbent and its application for defluoridation of drinking water[J].Journal of Hazardous Materials,2010,179(1):424-430.
[15]CHORNII V,NEDILKO S G,MIROSHNICHENKO M,et al.Influence of fluorination on structure and luminescence of ZrO2:Eu nanocrystals[J].Materials Research Bulletin,2017,90:237-243.
[16]徐孝义,张大超,董冰岩,等.高氟高氯酸性废水处理试验研究[J].江西理工大学学报,2015,36(3):13-18.
[17]张阳.电气石去除饮用水中卤族元素研究[D].长春:吉林大学,2012.
[18]郜玉楠,周历涛,王静,等.壳聚糖/沸石分子筛复合吸附颗粒的制备与性能[J].复合材料学报,2019,36(3):701-707.
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