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

doi:10.15541/jim20180536

Abstract

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)

CLC Number:

X705

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.

Figures/Tables 9

Fig. 1 XRD patterns of HT-SiC and SSZ-13/HT-SiC composites synthesized by using (a) TMAdaOH and (b) Cu-TEPA as template

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

Fig. 3 SEM images of pure Cu/SSZ-13 and Cu/SSZ-13/HT-SiC composites prepared by using Cu-TEPA as template

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

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

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

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

Fig. 7 Thermal stability of Cu(1)-SSZ-13/HT-SiC, Cu(5)/SSZ-13 and Cu(4)-SSZ-13 catalysts

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

References 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/SiC-waste Composite: Synthesis and Application for NH₃-SCR

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 9

References 35

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	HE Guoqiang, ZHANG Kaiheng, WANG Zhentao, BAO Jian, XI Zhaochen, FANG Zhen, WANG Changhao, WANG Wei, WANG Xin, JIANG Jiapei, LI Xiangkun, ZHOU Di. Ba(Nd_1/2Nb_1/2)O₃: Au Underrated K40 Microwave Dielectric Ceramic [J]. Journal of Inorganic Materials, 2025, 40(6): 639-646.
[2]	CHEN Yi, QIU Haipeng, CHEN Mingwei, XU Hao, CUI Heng. SiC/SiC Composite: Matrix Boron Modification and Mechanical Properties [J]. Journal of Inorganic Materials, 2025, 40(5): 504-510.
[3]	LI Jianjun, CHEN Fangming, ZHANG Lili, WANG Lei, ZHANG Liting, CHEN Huiwen, XUE Changguo, XU Liangji. Peroxymonosulfate Activation by CoFe₂O₄/MgAl-LDH Catalyst for the Boosted Degradation of Antibiotic [J]. Journal of Inorganic Materials, 2025, 40(4): 440-448.
[4]	MU Shuang, MA Qin, ZHANG Yu, SHEN Xu, YANG Jinshan, DONG Shaoming. Oxidation Behavior of Yb₂Si₂O₇ Modified SiC/SiC Mini-composites [J]. Journal of Inorganic Materials, 2025, 40(3): 323-328.
[5]	YANG Shuqi, YANG Cunguo, NIU Huizhu, SHI Weiyi, SHU Kewei. GeP₃/Ketjen Black Composite: Preparation via Ball Milling and Performance as Anode Material for Sodium-ion Batteries [J]. Journal of Inorganic Materials, 2025, 40(3): 329-336.
[6]	CHEN Guangchang, DUAN Xiaoming, ZHU Jinrong, GONG Qing, CAI Delong, LI Yuhang, YANG Donglei, CHEN Biao, LI Xinmin, DENG Xudong, YU Jin, LIU Boya, HE Peigang, JIA Dechang, ZHOU Yu. Advanced Ceramic Materials in Helicopter Special Structures: Research Progress and Application Prospect [J]. Journal of Inorganic Materials, 2025, 40(3): 225-244.
[7]	MU Haojie, ZHANG Yuanjiang, YU Bin, FU Xiumei, ZHOU Shibin, LI Xiaodong. Preparation and Properties of ZrO₂ Doped Y₂O₃-MgO Nanocomposite Ceramics [J]. Journal of Inorganic Materials, 2025, 40(3): 281-289.
[8]	WANG Yue, WANG Xin, YU Xianli. Room-temperature Ferromagnetic All-carbon Films Based on Reduced Graphene Oxide [J]. Journal of Inorganic Materials, 2025, 40(3): 305-313.
[9]	LUAN Xingang, HE Dianwei, TU Jianyong, CHENG Laifei. 2D Plain and 3D Needle-punched C/SiC Composites: Low-velocity Impact Damage Behavior and Failure Mechanism [J]. Journal of Inorganic Materials, 2025, 40(2): 205-214.
[10]	WANG Wenting, XU Jingjun, MA Ke, LI Meishuan, LI Xingchao, LI Tongqi. Oxidation Behavior at 1000-1300 ℃ in air of Ti₂AlC-20TiB₂ Synthesized by in-situ Reaction/Hot Pressing [J]. Journal of Inorganic Materials, 2025, 40(1): 31-38.
[11]	LIU Pengdong, WANG Zhen, LIU Yongfeng, WEN Guangwu. Research Progress on the Application of Silicon Slurry in Lithium-ion Batteries [J]. Journal of Inorganic Materials, 2024, 39(9): 992-1004.
[12]	QUAN Wenxin, YU Yiping, FANG Bing, LI Wei, WANG Song. Oxidation Behavior and Meso-macro Model of Tubular C/SiC Composites in High-temperature Environment [J]. Journal of Inorganic Materials, 2024, 39(8): 920-928.
[13]	MA Binbin, ZHONG Wanling, HAN Jian, CHEN Liangyu, SUN Jingjing, LEI Caixia. ZIF-8/TiO₂ Composite Mesocrystals: Preparation and Photocatalytic Activity [J]. Journal of Inorganic Materials, 2024, 39(8): 937-944.
[14]	HE Sizhe, WANG Junzhou, ZHANG Yong, FEI Jiawei, WU Aimin, CHEN Yifeng, LI Qiang, ZHOU Sheng, HUANG Hao. Fe/Submicron FeNi Soft Magnetic Composites with High Working Frequency and Low Loss [J]. Journal of Inorganic Materials, 2024, 39(8): 871-878.
[15]	WU Xiangquan, TENG Jiachen, JI Xiangxu, HAO Yubo, ZHANG Zhongming, XU Chunjie. Textured Porous Al₂O₃-SiO₂ Composite Ceramic Platelet-sphere Slurry: Characteristics and Simulation of Light Intensity Distribution [J]. Journal of Inorganic Materials, 2024, 39(7): 769-778.