Ce Modification on Mn/TiO2/cordierite Monolithic Catalyst for Low-temperature NOx Reduction†

doi:10.7503/cjcu20130971

Abstract

Abstract:

Cordierite monolithic catalysts were prepared firstly by sol-gel method for TiO₂/cordierite, then by impregnation method for Mn-Ce/TiO₂/cordierite monolithic catalyst and used for low-temperature selective catalytic reduction(SCR) of NO_x with ammonia. The results indicated that the activity of catalysts significantly improved after Ce doping. The conversion of NO could be improved by doping Ce from 71.1% to 97.6% at 120 ℃ with a gas hourly space velocity(GHSV) of 6000 h^-1. The catalyst of adding proper Ce had larger specific surface area and pore volume. The XPS, NH₃ adsorption and NO oxidation tests showed that the catalyst of adding proper Ce contained higher levels of Mn⁴⁺ and more chemical adsorption oxygen, which promoted NH₃ adsorption and NO oxidation activity. These factors may lead to the increasing of the SCR activity on Mn-Ce/TiO₂/CC catalyst.

Key words: Low temperature NOx reduction, Selective catalytic reduction(SCR), Cordierite, Cerium, TiO2

CLC Number:

O643

TrendMD:

LIU Jiandong, HUANG Zhanggen, LI Zhe, GUO Qianqian, LI Qiaoyan. Ce Modification on Mn/TiO₂/cordierite Monolithic Catalyst for Low-temperature NO_x Reduction^†[J]. Chem. J. Chinese Universities, 2014, 35(3): 589.

Figures/Tables 9

Fig.1 Influence of Ce on the catalytic activity of Mn-Ce(x)/TiO2/CC catalysts a. Mn/TiO2/CC; b. Mn-Ce(0.10)/TiO2/CC; c. Mn-Ce(0.15)/TiO2/CC; d. Mn-Ce(0.40)/TiO2/CC.

Table 1 Physical characteristic of the samples

Sample	S_BET/(m²·g^-1)	V_t/(cm³·g^-1)	V_micro/(cm³·g^-1)	D_p/nm
Untreated cordierite		0.0003		6.80
Pretreated cordierite with ammonia	42	0.0236	0.0079	2.27
TiO₂/CC	43	0.0390	0.0071	3.64
Mn/TiO₂/CC	42	0.0379	0.0055	3.62
Mn-Ce(0.10)/TiO₂/CC	43	0.0385	0.0061	3.68
Mn-Ce(0.15)/TiO₂/CC	45	0.0401	0.0065	3.57
Mn-Ce(0.40)/TiO₂/CC	39	0.0354	0.0054	3.66
TiO₂	59	0.0894		6.08

Fig.2 Mn2p(A), Ce3d(B), O1s(C) and Ti2p(D) XPS spectra of monolithic catalysts a. Mn/TiO2/CC; b. Mn-Ce(0.15)/TiO2/CC.

Table 2 XPS results of monolithic catalysts

Catalyst	Surface atomic content(%)				Molar ratio of Mn⁴⁺/(Mn³⁺+Mn⁴⁺)	Molar ratio of O_α/(O_α+O_β)
Catalyst	Ce			Mn	Ti	O
Mn/TiO₂/CC		13.76	15.96	70.28	0.60	0.16
Mn-Ce(0.15)/TiO₂/CC	5.89	8.60	14.78	70.73	0.76	0.31

Table 3 Total loading and surface chemical composition of different catalysts

Catalyst	Mass fraction by ICP(%)		Surface atomic content by XPS(%)
Catalyst	Mn	Ce	Mn	Ce
Mn/TiO₂/CC	1.18		13.76
Mn-Ce(0.15)/TiO₂/CC	1.12	0.52	8.60	5.89

Fig.3 NH3 adsorption of monolithic catalysts at 120 ℃ a. Mn/TiO2/CC; b. Mn-Ce(0.15)/TiO2/CC.

Fig.4 NH3 transient response of the SCR reaction over monolithic catalysts at 120 ℃a. Mn/TiO2/CC; b. Mn-Ce(0.15)/TiO2/CC. Reaction conditions: 0.05% NO, 0.05% NH3, 5% O2, balanced by N2, 400 mL/min of total flow rate; GHSV=6000 h-1.

Fig.5 Oxidation activity of NO to NO2 by O2 on the monolithic catalysts a. Mn/TiO2/CC; b. Mn-Ce(0.15)/TiO2/CC.

Fig.6 H2-TPR profile of Mn/TiO2/CC(a) and Mn-Ce(0.15)/TiO2/CC(b)catalysts

References 23

[1]	Qi G., Yang R. T., J. Phys. Chem. B,2004, 108(40), 15738—15747
[2]	Twigg M. V., Appl. Catal. B, 2007, 70(1), 2—15
[3]	Lietti L., Ramis G., Berti F., Appl. Catal. B,1998, 18(1), 1—36
[4]	Zheng Z. H., Tong H., Tong Z. Q., Huang Y., Luo Y., Journal of Fuel Chemistry and Technology,2010, 38(3), 343—351
	(郑足红, 童华, 童志权, 黄妍, 罗英. 燃料化学学报, 2010, 38(3), 343—351)
[5]	Huang Z., Zhu Z., Liu Z., Appl. Catal. B,2002, 39(4), 361—368
[6]	Peña D. A., Uphade B. S., Reddy E. P., Smirniotis P. G., J. Phys. Chem. B,2004, 108(28), 9927—9936
[7]	Pena D. A., Uphade B. S., Smirniotis P. G., J. Catal., 2004, 221(2), 421—431
[8]	Smirniotis P. G., Pena D. A., Uphade B. S., Angew. Chem. Int. Ed., 2001, 40(13), 2479—2482
[9]	Qi G., Yang R. T., J. Catal., 2003, 217(2), 434—441
[10]	Long R. Q., Yang R. T., J. Am. Chem. Soc., 1999, 121(23), 5595—5596
[11]	Long R., Yang R., Appl. Catal. B,2000, 27(2), 87—95
[12]	Wu Z., Jiang B., Liu Y., Zhao W., Guan B., J. Hazard. Mater., 2007, 145(3), 488—494
[13]	Wu Z., Jin R., Liu Y., Wang H., Catal. Commun., 2008, 9(13), 2217—2220
[14]	Zhang X., Ji L., Zhang S., Yang W., J. Power Sources,2007, 173(2), 1017—1023
[15]	Romeo M., Bak K., El Fallah J., Le Normand F., Hilaire L., Surf. Interface Anal., 1993, 20(6), 508—512
[16]	Kang M., Park E. D., Kim J. M., Yie J. E., Appl. Catal. B,2007, 327(2), 261—269
[17]	Yang S., Zhu W., Jiang Z., Chen Z., Wang J., Appl. Surf. Sci., 2006, 252(24), 8499—8505
[18]	Jing L., Xu Z., Sun X., Shang J., Cai W., Appl. Surf. Sci., 2001, 180(3), 308—314
[19]	He L. F., Liu J. D., Huang W., Li Z., Chem. J. Chinese Universities,2012, 33(11), 2532—2536
	(贺丽芳, 刘建东, 黄伟, 李哲. 高等学校化学学报, 2012, 33(11), 2532—2536)
[20]	Busca G., Lietti L., Ramis G., Berty F., Appl. Catal. B,1998, 18(1/2), 1—36
[21]	Yao S. M., Zhang J. W., Guo X., Qiu X. P., Chem. Res. Chinese Universities,2013, 29(2), 307—310
[22]	Long R., Yang R., J. Catal., 2001, 198(1), 20—28
[23]	Koebel M., Madia G., Elsener M., Catal. Today,2002, 73(3), 239—247

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Ce Modification on Mn/TiO₂/cordierite Monolithic Catalyst for Low-temperature NO_x Reduction^†

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