Cu-SSZ-13/碳化硅废料复合材料的合成及其 NH3-SCR性能研究

doi:10.15541/jim20180536

无机材料学报 ›› 2019, Vol. 34 ›› Issue (9): 953-960.DOI: 10.15541/jim20180536 CSTR: 32189.14.10.15541/jim20180536

Cu-SSZ-13/碳化硅废料复合材料的合成及其
NH₃-SCR性能研究

罗清¹,苑青^1,²(),蒋前勤¹,于乃森¹

1.大连民族大学国家民委新能源与稀土资源利用重点实验室, 辽宁省光电材料与器件重点实验室, 大连 116600
2.中国科学院大连化学物理研究所催化基础国家重点实验室, 大连 116023

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:
大连民族大学自主科研基金(DC201502080409);大连民族大学大学生创新创业训练计划项目(201812026149)

Cu-SSZ-13/SiC-waste Composite: Synthesis and Application for NH₃-SCR

LUO Qing¹,YUAN Qing^1,²(),JIANG Qian-Qin¹,YU Nai-Sen¹

1.Key Laboratory of Photosensitive Materials & Devices of Liaoning Province, Key Laboratory of New Energy and Rare Earth Resource Utilization of State Ethnic Affairs Commission, Dalian Minzu University, Dalian 116600, China
2.State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

Received:2018-11-19 Revised:2019-03-04 Published:2019-09-20 Online:2019-05-13
Supported by:
Fundamental Research Funds for the Central Universities(DC201502080409);Training Program of Innovation and Entrepreneurship for Undergraduates in Dalian Minzu University(201812026149)

摘要/Abstract

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。

关键词: SSZ-13, 复合材料, 碳化硅废料, 氨气选择性催化还原

Abstract:

Solar cell wafer cutting process produces a lot of silicon carbide-based waste named HT-SiC. Herein, we developed a novel catalyst through a one-pot hydrothermal process combined with an ion-exchange method to synthesize Cu-SSZ-13/HT-SiC composite and applied in denitration catalytic reaction. TMAdaOH and Cu-TEPA were used as templates to prepare the precursor for Cu-SSZ-13, respectively. Results showed that, with participation of HT-SiC, SSZ-13 crystal was successfully obtained by using TMAdaOH template, while it would get only amorphous structure by using Cu-TEPA template. NH₃-SCR(Selective Catalytic Reduction, SCR) exhibited catalytic activity and stability of Cu-SSZ-13/HT-SiC in medium and high temperature zones was more effective than those of Cu-SSZ-13 without HT-SiC, and NO consumption by the former was about 11-fold of the latter at 500 ℃. Moreover, compared with Cu-SSZ-13/α-SiC catalyst prepared with pure SiC (α-SiC), Cu-SSZ-13/HT-SiC shows better catalytic activity in the whole temperature range. These favorable performances are attributed not only to the good thermal conductivity and thermal stability of SiC, but also to the 7.34wt% Fe component contained in HT-SiC, which acts as an active site for reducing NO in NH₃-SCR. This method not only provides a way to reuse the SiC waste, but also enhances denitrification activity of Cu-SSZ-13 in medium and high operating temperature.

Key words: SSZ-13, composite, silicon carbide waste, NH₃-selective catalytic reduction (NH₃-SCR)

中图分类号:

X705

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/表 9

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

图4 纯相SSZ-13、HT-SiC和SSZ-13/HT-SiC复合物的N2吸附/脱附等温线

Fig. 4 N2 adsorption/desorption isotherms of pure SSZ-13, HT-SiC and SSZ-13/HT-SiC composites

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	S_BET/(m²·g^-1)	S_mic/(m²·g^-1)	S_ext/(m²·g^-1)	V_t/(cm³·g^-1)^a	V_mic/(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5 纯相SSZ-13、HT-SiC和SSZ-13/HT-SiC-0.8 g复合物的热导率曲线

Fig. 5 Thermal conductivity of HT-SiC, SSZ-13/HT-SiC-0.8 g composite and pure SSZ-13

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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Cu-SSZ-13/碳化硅废料复合材料的合成及其
NH₃-SCR性能研究

Cu-SSZ-13/SiC-waste Composite: Synthesis and Application for NH₃-SCR

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