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

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

参考文献 35

[1]	LIU H Y, MA X, LI B W ,et al. Combustion and emission characteristics of a direct injection diesel engine fueled with biodiesel and PODE/biodiesel fuel blends. Fuel, 2017,209:62-68.
[2]	ELSANUSI O A, ROY M M, SIDHU M S . Experimental investigation on a diesel engine fueled by diesel-biodiesel blends and their emulsions at various engine operating conditions. Appl. Energy, 2017,203:582-593.
[3]	LIU F D, YU Y B, HE H . Environmentally-benign catalysts for the selective catalytic reduction of No_x from diesel engines: structure- activity relationship and reaction mechanism aspects. Chem. Commun., 2014,50(62):8445-8463
[4]	BEALE A M, GAO F, LEZCANO-GONZALEZ I ,et al. Recent advances in automotive catalysis for NO_x emission control by small-pore microporous materials. Chem. Soc. Rev., 2015,44(20):7371-7405.
[5]	ANGGARA T, PAOLUCCI C, SCHNEIDER W F . Periodic DFT characterization of NO_x adsorption in Cu-Exchanged SSZ-13 zeolite catalysts. J. Phys. Chem. C, 2016,120(49):27934-27943.
[6]	SHWAN S, JANSSON J, OLSSON L ,et al. Chemical deactivation of H-BEA and Fe-BEA as NH₃-SCR catalysts—effect of potassium. Appl. Catal. B-Environ., 2015,166:277-286.
[7]	WANG H Y, WANG B D, SUN Q ,et al. New insights into the promotional effects of Cu and Fe over V₂O₅-WO₃/TiO₂ NH₃-SCR catalysts towards oxidation of Hg⁰. Catal. Commun., 2017,100:169-172.
[8]	WANG J H, ZHAO H W, HALLER G ,et al. Recent advances in the selective catalytic reduction of NO_x with NH₃ on Cu-Chabazite catalysts. Appl. Catal. B-Environ., 2017,202:346-354.
[9]	FICKEL D W, D'ADDIO E, LAUTERBACH J A , et al. The ammonia selective catalytic reduction activity of copper-exchanged small-pore zeolites. Appl. Catal. B-Environ., 2011,102(3/4):441-448.
[10]	SZANYI J, KWAK J H, ZHU H Y ,et al. Characterization of Cu-SSZ-13 NH₃ SCR catalysts: an in situ FT-IR study. Phys. Chem. Chem. Phys., 2013,15(7):2368-2380.
[11]	GUNTER T, PESEK J, SCHAFER K ,et al. Cu-SSZ-13 as pre-turbine NO_x-removal-catalyst: impact of pressure and catalyst poisons. Appl. Catal. B-Environ., 2016,198:548-557.
[12]	MASIH D, ROHANI S, KONDO J N ,et al. Low-temperature methanol dehydration to dimethyl ether over various small-pore zeolites. Appl. Catal. B-Environ., 2017,217:247-255.
[13]	ZHENG Y H, HU N, WANG H M ,et al. Preparation of steam-stable high-silica CHA (SSZ-13) membranes for CO₂/CH₄ and C₂H₄/C₂H₆ separation. J. Membrane Sci., 2015,475:303-310.
[14]	OORD R, TEN HAVE I C, ARENDS J M , et al. Enhanced activity of desilicated Cu-SSZ-13 for the selective catalytic reduction of NO_x and its comparison with steamed Cu-SSZ-13. Catal. Sci. Technol., 2017,7(17):3851-3862.
[15]	CHINTALA V, SUBRAMANIAN K A . Hydrogen energy share improvement along with NO_x(oxides of nitrogen) emission reduction in a hydrogen dual-fuel compression ignition engine using water injection. Energy. Convers. Manage., 2014,83:249-259.
[16]	KAWAMURA T, HORI D, KANGAWA Y ,et al. Thermal conductivity of SiC calculated by molecular dynamics. Jpn. J. Appl. Phys., 2008,47(12):8898-8901.
[17]	ZHAO L, KONG L P, LIU C Z ,et al. AgCu/SiC-powder: a highly stable and active catalyst for gas-phase selective oxidation of alcohols. Catal. Commun., 2017,98:1-4.
[18]	WANG H, SCMACK R, PAUL B ,et al. Porous silicon carbide as a support for Mn/Na/W/SiC catalyst in the oxidative coupling of methane. Appl. Catal. A-Gen., 2017,537:33-39.
[19]	DUONG-VIET C, TRUONG-PHUOC L, TRAN-THANH T ,et al. Nitrogen-doped carbon nanotubes decorated silicon carbide as a metal-free catalyst for partial oxidation of H₂S. Appl. Catal. A-Gen., 2014,482:397-406.
[20]	ZHOU T Y, YUAN Q, PAN X L ,et al. Growth of Cu/SSZ-13 on SiC for selective catalytic reduction of NO with NH₃. Chinese J. Catal., 2018,39(1):71-78.
[21]	MARTIN N, VENNESTROM P N R, THOGERSEN J R , et al. Fe-containing zeolites for NH₃-SCR of NO_x: effect of structure, synthesis procedure, and chemical composition on catalytic performance and stability. Chem. -Eur. J., 2017,23(54):13404-13414.
[22]	REN Z Y, FAN H, WANG R . A novel ring-like Fe₂O₃-based catalyst: tungstophosphoric acid modification, NH₃-SCR activity and tolerance to H₂O and SO₂. Catal. Commun., 2017,100:71-75.
[23]	SHISHKIN A, KANNISTO H, CARLSSON P A ,et al. Synthesis and functionalization of SSZ-13 as an NH₃-SCR catalyst. Catal. Sci. Technol., 2014,4(11):3917-3926.
[24]	XU R N, ZHANG R D, LIU N ,et al. Template design and economical strategy for the synthesis of SSZ-13 (CHA-Type) zeolite as an excellent catalyst for the selective catalytic reduction of NO_x by ammonia. ChemCatChem, 2015,7(23):3842-3847.
[25]	REN L M, ZHU L F, YANG C G , et al. Designed copper-amine complex as an efficient template for one-pot synthesis of Cu-SSZ-13 zeolitewith excellent activity for selective catalytic reduction of NO_x by NH₃. Chem. Commun., 2011,47(35):9789-9791.
[26]	XIE K P, WOO J, BERNIN D ,et al. Insights into hydrothermal aging of phosphorus-poisoned Cu-SSZ-13 for NH₃-SCR. Appl. Catal. B-Environ., 2018,241:205-216.
[27]	WANG J, SHAO L, WANG C ,et al. Controllable preparation of various crystal size and nature of intra-crystalline diffusion in Cu/SSZ-13 NH₃-SCR catalysts. J. Catal., 2018,367:221-228.
[28]	HAN L N, ZHAO X G, YU H F ,et al. Preparation of SSZ-13 zeolites and their NH₃-selective catalytic reduction activity. Micropor. Mesopor. Mater., 2018,261:126-136.
[29]	TAKATA T, TSUNOJI N, TAKAMITSU Y ,et al. Nanosized CHA zeolites with high thermal and hydrothermal stability derived from the hydrothermal conversion of FAU zeolite. Micropor. Mesopor. Mater., 2016,225:524-533.
[30]	GE S B, GENG W C, HE X W ,et al. Effect of framework structure, pore size and surface modification on the adsorption performance of methylene blue and Cu²⁺ in mesoporous silica. Colloid Surface A, 2018,539:154-162.
[31]	GAO F, WASHTON N M, WANG Y L ,et al. Effects of Si/Al ratio on Cu/SSZ-13 NH₃-SCR catalysts: implications for the active Cu species and the roles of Brønsted acidity. J. Catal., 2015,331:25-38.
[32]	OHLIN L, BEREZOVSKY V, OBERG S ,et al. Effect of water on the adsorption of methane and carbon dioxide in zeolite Na-ZSM-5 studied using in situ ATR-FT-IR spectroscopy. J. Phys. Chem. C, 2016,120(51):29144-29152.
[33]	GENG W C, GE S B, HE X W ,et al. Volatile organic compound gas-sensing properties of bimodal porous α-Fe₂O₃ with ultrahigh sensitivity and fast response. ACS Appl. Mater. Interfaces, 2018,10(16):13702-13711.
[34]	YU L M, ZHONG Q, ZHANG S L . Research of copper contained SAPO-34 zeolite for NH₃-SCR DeNO_x by solvent-free synthesis with Cu-TEPA. Micropor. Mesopor. Mater., 2016,234:303-309.
[35]	ZHANG T, CHANG H Z, YOU Y C ,et al. Excellent activity and selectivity of one-pot synthesized Cu SSZ-13 catalyst in the selective catalytic oxidation of ammonia to nitrogen. Environ. Sci. Technol., 2018,52(8):4802-4808.

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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