无机材料学报 ›› 2019, Vol. 34 ›› Issue (9): 953-960.DOI: 10.15541/jim20180536
收稿日期:
2018-11-19
修回日期:
2019-03-04
出版日期:
2019-09-20
网络出版日期:
2019-05-13
作者简介:
罗 清(1996-), 男, 本科生. E-mail: 2792206808@qq.com
基金资助:
LUO Qing1,YUAN Qing1,2(),JIANG Qian-Qin1,YU Nai-Sen1
Received:
2018-11-19
Revised:
2019-03-04
Published:
2019-09-20
Online:
2019-05-13
Supported by:
摘要:
太阳能电池硅片切割工艺中使用碳化硅作为切割硅片的磨料, 切割后会形成大量的废料-一种碳化硅基混合物(HT-SiC), 其中含有少量金属等杂质。本工作开发了一种新型催化剂, 将Cu-SSZ-13分子筛和HT-SiC通过水热法结合离子交换制备成一种复合材料Cu-SSZ-13/HT-SiC, 并应用于脱硝催化反应。在合成Cu-SSZ-13分子筛时使用两种模板剂: N, N, N-三甲基-1-铵金刚烷(TMAdaOH)和铜胺络合物(Cu-TEPA)。实验结果表明, 在HT-SiC的参与下, TMAdaOH模板成功得到SSZ-13晶体, 而使用Cu-TEPA模板得到的可能是非晶态结构。在NH3-SCR反应中, 结果显示, Cu-SSZ-13/HT-SiC在中高温区间相比纯相Cu-SSZ-13更加出色, 在500 ℃时, 前者的NO消耗量约为后者的11倍。另外, 相比于用纯相SiC(α-SiC)合成的Cu-SSZ-13/α-SiC催化剂, Cu-SSZ-13/HT-SiC在整个温度区间的催化活性表现更佳。这些良好的性能不仅归因于SiC良好的导热性和热稳定性, 而且归因于HT-SiC中存在的少量Fe组分, 在脱硝催化反应中充当了还原NO的活性位点。该方法不仅解决了废弃磨料环境污染的问题, 也为重复利用SiC废料提供了新的途径。
中图分类号:
罗清,苑青,蒋前勤,于乃森. Cu-SSZ-13/碳化硅废料复合材料的合成及其
NH3-SCR性能研究[J]. 无机材料学报, 2019, 34(9): 953-960.
LUO Qing,YUAN Qing,JIANG Qian-Qin,YU Nai-Sen. Cu-SSZ-13/SiC-waste Composite: Synthesis and Application for NH3-SCR[J]. Journal of Inorganic Materials, 2019, 34(9): 953-960.
图1 HT-SiC和分别用(a)TMAdaOH、(b)Cu-TEPA为模板合成的SSZ-13/HT-SiC复合物的XRD图谱
Fig. 1 XRD patterns of HT-SiC and SSZ-13/HT-SiC composites synthesized by using (a) TMAdaOH and (b) Cu-TEPA as template
图2 HT-SiC和以TMAdaOH为模板合成的SSZ-13/HT-SiC复合物的SEM照片, 插图为孔径分布图
Fig. 2 SEM images of HT-SiC and SSZ-13/HT-SiC composites synthesized by using TMAdaOH as template with insets showing corresponding partiesize distributions
图3 以Cu-TEPA为模板合成的纯相Cu/SSZ-13和Cu/SSZ-13/HT-SiC复合物的SEM照片
Fig. 3 SEM images of pure Cu/SSZ-13 and Cu/SSZ-13/HT-SiC composites prepared by using Cu-TEPA as template
Sample | SBET/(m2·g-1) | Smic/(m2·g-1) | Sext/(m2·g-1) | Vt/(cm3·g-1)a | Vmic/(cm3·g-1)b |
---|---|---|---|---|---|
HT-SiC | 0.5 | 0.4 | 0.006 | - | - |
SSZ-13 | 567.7 | 560.1 | 7.600 | 0.31 | 0.30 |
SSZ-13/HT-SiC-0.4 g | 0.9 | 0.8 | 0.010 | - | - |
SSZ-13/HT-SiC-0.6 g | 226.5 | 223.4 | 3.000 | 0.12 | 0.11 |
SSZ-13/HT-SiC-0.8 g | 378.5 | 373.4 | 5.100 | 0.21 | 0.20 |
SSZ-13/HT-SiC-1.0 g | 355.7 | 350.9 | 4.800 | 0.19 | 0.18 |
表1 HT-SiC载体、SSZ-13和SSZ-13/HT-SiC复合材料的结构性质
Table 1 Textural properties of HT-SiC support, SSZ-13 and SSZ-13/HT-SiC composites
Sample | SBET/(m2·g-1) | Smic/(m2·g-1) | Sext/(m2·g-1) | Vt/(cm3·g-1)a | Vmic/(cm3·g-1)b |
---|---|---|---|---|---|
HT-SiC | 0.5 | 0.4 | 0.006 | - | - |
SSZ-13 | 567.7 | 560.1 | 7.600 | 0.31 | 0.30 |
SSZ-13/HT-SiC-0.4 g | 0.9 | 0.8 | 0.010 | - | - |
SSZ-13/HT-SiC-0.6 g | 226.5 | 223.4 | 3.000 | 0.12 | 0.11 |
SSZ-13/HT-SiC-0.8 g | 378.5 | 373.4 | 5.100 | 0.21 | 0.20 |
SSZ-13/HT-SiC-1.0 g | 355.7 | 350.9 | 4.800 | 0.19 | 0.18 |
图6 (a) HT-SiC、用TMAdaOH 或 Cu-TEPA模板合成的Cu-SSZ-13和Cu-SSZ-13/HT-SiC复合物的NH3-SCR测试; (b) Cu(1)-SSZ-13/HT-SiC、Cu(4)-SSZ-13和Cu(5)/SSZ-13三种催化剂每克Cu每分钟所消耗NO的摩尔数
Fig. 6 (a) Denitrification activity of HT-SiC, Cu-SSZ-13 and Cu-SSZ-13/HT-SiC catalysts synthesized by using TMAdaOH or Cu-TEPA as template with different Cu contents; (b) The mole of NO consumed (molNO/(gCu·min)) by Cu(1)-SSZ-13/HT-SiC, Cu(4)-SSZ-13 and Cu(5)/SSZ-13 catalysts
图7 Cu(1)-SSZ-13/HT-SiC, Cu(5)/SSZ-13 和 Cu(4)-SSZ-13 催化剂的热稳定性测试结果
Fig. 7 Thermal stability of Cu(1)-SSZ-13/HT-SiC, Cu(5)/SSZ-13 and Cu(4)-SSZ-13 catalysts
图8 三次循环脱硝测试后Cu(1)-SSZ-13/HT-SiC和Cu(4)-SSZ-13 催化剂的N2吸附/脱附等温线
Fig. 8 N2 adsorption/desorption isotherms of Cu(1)-SSZ-13/HT-SiC and Cu(4)-SSZ-13 catalysts after three-cycle NH3-SCR test
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