W掺入对Ti0.8Zr0.2Ce0.2O2.4/Al2O3-TiO2-SiO2催化脱硝性能的优化

doi:10.15541/jim20140196

无机材料学报 ›› 2014, Vol. 29 ›› Issue (12): 1294-1300.DOI: 10.15541/jim20140196 CSTR: 32189.14.10.15541/jim20140196

W掺入对Ti_0.8Zr_0.2Ce_0.2O_2.4/Al₂O₃-TiO₂-SiO₂催化脱硝性能的优化

付伟良, 沈岳松, 祝社民, 沈树宝

(南京工业大学材料科学与工程学院, 南京 210009)

收稿日期:2014-04-13 修回日期:2014-06-08 出版日期:2014-12-20 网络出版日期:2014-11-20
作者简介:付伟良(1990–), 男, 硕士研究生. E-mail: gnailiewuf@163.com
基金资助:
江苏省环保科研课题(2012016);国家自然科学基金(21106071, 51272105);国家科技支撑计划(2012BAE01B03);教育部博士点基金(20113221120004);江苏省社会发展科技支撑计划(BE2013718)

Promotional Effect of Tungsten Incorporation on Catalytic Performance of Ti_0.8Zr_0.2Ce_0.2O_2.4/Al₂O₃-TiO₂-SiO₂ for Selective Catalytic Reduction of NO_x by NH₃

FU Wei-Liang, SHEN Yue-Song, ZHU She-Min, SHEN Shu-Bao

(College of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009, China)

Received:2014-04-13 Revised:2014-06-08 Published:2014-12-20 Online:2014-11-20
About author:FU Wei-Liang. E-mail: gnailiewuf@163.com
Supported by:
Research Subject of Environmental Protection Department of Jiangsu Province of China (2012016);National Natural Science Foundation of China (21106071, 51272105);National Key Technology R&D Program of China (2012BAE01B03);New Teachers’ Fund for Doctor Stations Sponsored by the Ministry of Education of China (20113221120004);Jiangsu Provincial Science and Technology Supporting Program (BE2013718)

摘要/Abstract

摘要：

以Al₂O₃-TiO₂-SiO₂(ATS)为载体、Ti_0.8Zr_0.2Ce_0.2O_2.4(TZC)为催化活性组分, 采用挤出成型法制备系列整体式TZC/ATS及W掺入催化剂样品。研究了W掺入对催化剂TZC/ATS 的氨气选择性催化还原(NH₃-SCR)脱除NO活性及抗K₂O、CaO等毒性的影响, 比较了Ti_0.8Zr_0.2Ce_0.2W_0.08O_2.64/ATS(TZCW_0.4/ATS)催化剂与V₂O₅(WO₃)/TiO₂催化剂的抗K₂O、CaO等中毒性能, 并采用N₂-BET、XRD、SEM和NH₃-TPD等技术手段分别表征了催化剂的比表面积、固相结构、微观形貌及表面酸性。结果表明, 当活性组分中Ti/Zr/Ce/W元素摩尔比为4:1:1:0.4时, TZCW_0.4/ATS催化剂NH₃-SCR脱除NO的效率最高、稳定性最好。W掺入显著增强了催化剂的抗K₂O及CaO毒性能力, 且TZCW_0.4/ATS催化剂抗K₂O及CaO的中毒能力明显强于V₂O₅(WO₃)/TiO₂催化剂。分析表明, W掺入提高了TZCW_0.4/ATS催化剂的比表面积, 增加了催化剂的表面酸量, 从而优化了催化剂的脱硝性能。

关键词: Ti0.8Zr0.2Ce0.2O2.4/Al2O3-TiO2-SiO2催化剂, W掺入, 水泥烟气脱硝, 抗K2O中毒, 抗CaO中毒

Abstract:

Series TZC/ATS catalysts and the tungsten-added samples, with Ti_0.8Zr_0.2Ce_0.2O_2.4 (TZC for short) as active component and Al₂O₃-TiO₂-SiO₂ (ATS for short) as catalyst carrier, were prepared by extrusion method. Effects of tungsten incorporation on catalytic performance and tolerance towards K₂O and CaO poisoning of TZC/ATS for deNO_x by NH₃ selective catalytic reduction (NH₃-SCR) were mainly studied, and anti K₂O and CaO poisoning abilities between the TZCW_0.4/ATS and the V₂O₅(WO₃)/TiO₂ were comparatively analyzed. Moreover, the specific surface, solid-phase structure, morphology and surface acidity of the catalysts were characterized by techniques of N₂-BET, XRD, SEM and NH₃-TPD, respectively. Results showed that the TZCW_0.4/ATS catalyst exhibited the highest catalytic activity and the best stability for deNO_x by NH₃-SCR when the Ti/Zr/Ce/W molar ratio of the active component was 4:1:1:0.4. Furthermore, tungsten incorporation greatly enhanced the anti K₂O and CaO poisoning abilities of the TZCW_0.4/ATS catalyst, and these anti-poisoning abilities of the TZCW_0.4/ATS were much stronger than those of the V₂O₅(WO₃)/TiO₂. The promotional effect on catalytic deNO_x performance was caused by increased specific surface area and enhanced surface acidity of the TZCW_0.4/ATS catalyst after tungsten incorporation.

Key words: Ti0.8Zr0.2Ce0.2O2.4/Al2O3-TiO2-SiO2 catalyst, tungsten incorporation, cement flue gas deNOx, anti K2O poisoning, anti CaO poisoning

中图分类号:

TB34

付伟良, 沈岳松, 祝社民, 沈树宝. W掺入对Ti_0.8Zr_0.2Ce_0.2O_2.4/Al₂O₃-TiO₂-SiO₂催化脱硝性能的优化[J]. 无机材料学报, 2014, 29(12): 1294-1300.

FU Wei-Liang, SHEN Yue-Song, ZHU She-Min, SHEN Shu-Bao. Promotional Effect of Tungsten Incorporation on Catalytic Performance of Ti_0.8Zr_0.2Ce_0.2O_2.4/Al₂O₃-TiO₂-SiO₂ for Selective Catalytic Reduction of NO_x by NH₃[J]. Journal of Inorganic Materials, 2014, 29(12): 1294-1300.

图/表 9

表 1 K2O、CaO中毒催化剂样品

Table 1 Catalysts loaded with different amounts of CaO

	Content/ wt%	TZC/ATS	TZCW_0.4/ATS
CaO	0.17	TZC/ATS-Ca_0.17	TZCW_0.4/ATS-Ca_0.17
	0.51	TZC/ATS-Ca_0.51	TZCW_0.4/ATS-Ca_0.51
	0.85	TZC/ATS-Ca_0.85	TZCW_0.4/ATS-Ca_0.85
	1.70	TZC/ATS-Ca_1.70	TZCW_0.4/ATS-Ca_1.70
K₂O	0.23	TZC/ATS-K_0.23	TZCW_0.4/ATS-K_0.23
	0.70	TZC/ATS- K_0.70	TZCW_0.4/ATS-K_0.70
	1.16	TZC/ATS- K_1.16	TZCW_0.4/ATS- K_1.16
	1.76	TZC/ATS-K_1.76	TZCW_0.4/ATS-K_1.76
	2.14	TZC/ATS- K_2.14	TZCW_0.4/ATS-K_2.14

图 1 反应温度对催化活性的影响

Fig. 1 Effect of reaction temperature on catalytic activity

图 2 CaO对催化脱硝活性的影响

Fig. 2 Effect of CaO on catalytic deNOx activity (a) TZC/ATS; (b) TZCW0.4/ATS; (c) 1%V2O5/TiO2[23]

图 3 K2O对催化脱硝活性的影响

Fig. 3 Effect of K2O on catalytic deNOx activity (XNO: NO conversion) (a) TZC/ATS; (b) TZCW0.4/ATS; (c) V2O5(WO3)/TiO2[24]

表 2 催化剂的比表面积、孔容和平均孔径

Table 2 Textual characteristics of catalyst samples

Sample	S_BET/(m²·g^-1)	V_pore/(cm³·g^-1)	d_pore/nm
TZC/ATS	84.29	0.185	8.771
TZCW_0.4/ATS	91.11	0.181	7.962
TZCW_0.4/ATS-K_1.76	89.16	0.185	8.297
TZCW_0.4/ATS-Ca_1.70	85.60	0.176	8.231

图 4 催化剂样品的扫描电镜照片

Fig. 4 SEM images of TZCW0.4/ATS

图 5 催化剂粉末XRD图谱

Fig. 5 XRD patterns of catalyst powders

图 6 催化剂的NH3-TPD图谱

Fig. 6 NH3-TPD profiles of catalyst samples

图 7 催化剂K2O及CaO化学中毒机理

Fig. 7 K2O and CaO poisoning mechanism

参考文献 29

[1]	BUSCA G, LIETTI L, RAMIS G, et al.Chemical and mechanistic aspects of the selective catalytic reduction of NOx by ammonia over oxide catalysts: a review. Appl. Catal B: Environ., 1998, 18(1/2): 1-36.
[2]	GAO ZHEN-NING, LIU GUO-CAI. The road of green twelfth five-year plan is under foot. Environmental economics, 2012(1): 16-33.
[3]	DUMESIC J A, TOPSOE N Y, TOPSOE H, et al.Kinetics of selective catalytic reduction of nitric oxide by ammonia over vanadia/titania. J. Catal., 1996, 163(2): 409-417.
[4]	CASAGRAND L, LIETTI L, NOVA I, et al.SCR of NO by NH3 over TiO2-supported V2O5-MoO3 catalysts: reactivity and redox behavior. Appl. Catal B: Environ., 1999, 22(1): 63-77.
[5]	LING XI-FENG, YANG RONG. Control effect on occupational hazards of a denitrification catalyst production base. Journal of Occ-upational Health and Damage, 2009, 24(3):131-133.
[6]	ZHOU YONG-KANG. Research on deNOx Technology of Flue Gas from Cement Kiln. The Proceedings of the Chinese Annual Conference on Cement Technology, 2012: 173-181.
[7]	FANG JING-RUI, MA ZHONG-CHENG, WANG LAN. Research progress on catalytic reduction technique for denitration of cement flue gas. Environmental Pollution & Control, 2013, 35(2): 85-92.
[8]	祝社民, 沈岳松. 一种以铝基陶瓷为载体的烟气脱硝整体式催化剂及其制备方法. 中国, B01J23/10, CN101234345A. 2008. 08. 06.
[9]	祝社民, 沈岳松, 许健, 等. 一种SCR烟气脱硝复合催化剂及其制备方法. 中国, B01J23/10, CN101352678A. 2009.01.28.
[10]	祝社民, 沈岳松, 余勇, 等. 以硅基陶瓷为载体的烟气脱硝整体式催化剂及其制备方法. 中国, B01J23/10, CN101357328A. 2009. 02. 04.
[11]	祝社民, 沈岳松, 周晨, 等. 一种烟气脱硝复合催化剂及其制备方法. 中国, B01D53/86, CN101380543A. 2009.03.11.
[12]	沈岳松, 祝社民. 一种蜂窝状SCR脱硝复合氧化物催化剂及其制备方法. 中国, B01D53/56, CN102008952A. 2011.04.13.
[13]	XU W Q, YU Y B, ZHANG C B, et al.Selective catalytic reduction of NO by NH3 over a Ce/TiO2 catalyst. Catal. Commun., 2008, 9(6): 1453-1457.
[14]	SHEN Y S, ZHU S M, QIU T, et al.A novel catalyst of CeO2/ Al2O3 for selective catalytic reduction of NO by NH3. Catal. Commun., 2009, 11(1): 20-23.
[15]	CASAPU M, KROCHER O, ELSENER M.Screening of doped MnOx-CeO2 catalysts for low-temperature NO-SCR. Appl. Catal B: Environ., 2009, 88(3/4): 413-419.
[16]	CHEN L, LI J H, GE M F, et al.Enhanced activity of tungsten modified CeO2/TiO2 for selective catalytic reduction of NOx with ammonia. Catal. Today, 2010, 153(3/4): 77-83.
[17]	CHEN L, LI J H, ABLIKIM W, et al.CeO2-WO3 mixed oxides for the selective catalytic reduction of NOx by NH3 over a wide temperature range. Catal. Lett., 2011, 141(12):1859-1864 .
[18]	WU DA-WANG, ZHANG QIU-LIN, LIN TAO, et al. Effect of Fe on the selective catalytic reduction of NO by NH3 at low temperature over Mn/CeO2-TiO2 catalyst. Journal of Inorganic Materials, 2012, 27(5): 495-500.
[19]	LIU C X, CHEN L, LI J H, et al.Enhancement of activity and sulfur resistance of CeO2 supported on TiO2-SiO2 for the selective catalytic reduction of NO by NH3. Environ. Sci. Technol., 2012, 46(11): 6182-6189.
[20]	SHEN Y S, MA Y F, ZHU S M.Promotional effect of zirconium additives on Ti0.8Ce0.2O2 for selective catalytic reduction of NO. Catal. Sci. Technol. 2012, 2(3): 589-599.
[21]	LIETTI L.Reactivity of V2O5-WO3/TiO2 de-NOx by transient- methods. Appl. Catal B: Environ., 1996. 10(4): 281-297
[22]	LI YE, CHENG HAO, LI DE-YI, et al. Tungsta promotion of selec- tive catalytic reduction of NOx by NH3 over ceria-zirconia catalyst. Chinese Journal of Catalysis, 2008, 29(6): 547-552.
[23]	李锋.以纳米TiO2为载体的燃煤烟气脱硝SCR催化剂的研究. 江苏: 东南大学博士学位论文, 2006.
[24]	KAMATA H, TAKAHASHI K, ODENBRAND C U I. The role of K2O in the selective reduction of NO with NH3 over a V2O5(WO3)/ TiO2 commercial selective catalytic reduction catalyst. J. Mol. Catal. A: Chem., 1999, 139(2/3): 189-198.
[25]	陆佩文.无机材料科学基础. 南京: 东南大学出版社, 1996: 67-67.
[26]	司知蠢.CuOx/WOx-ZrO2催化剂制备及其NH3-SCR 催化机理研究. 北京: 清华大学工学博士学位论文, 2010.
[27]	FOTTINGER K, ZORN K, VINEK H.Influence of the sulfate content on the activity of Pt containing sulfated zirconia. Appl. Catal A: General., 2005, 284(1/2): 69-75.
[28]	PEREIRA A L C, MARCHETTI S G, ALBORNOZ A, et al. Effect of iron on the properties of sulfated zirconia. Appl. Catal A: General., 2008, 334(1/2): 187-198.
[29]	HWANG C C, MOU C Y.Comparison of the promotion effect on sulfated mesoporous zirconia catalysts achieved by alumina and gallium. Appl. Catal A: General., 2009, 365(2): 173-179.

W掺入对Ti_0.8Zr_0.2Ce_0.2O_2.4/Al₂O₃-TiO₂-SiO₂催化脱硝性能的优化

Promotional Effect of Tungsten Incorporation on Catalytic Performance of Ti_0.8Zr_0.2Ce_0.2O_2.4/Al₂O₃-TiO₂-SiO₂ for Selective Catalytic Reduction of NO_x by NH₃

RichHTML

PDF (PC)

可视化