Effect of Potassium Loading on the NOx Storage and Reduction Performance of the CuO/K2CO3/MgAl2O4 Catalyst at High Temperature†

doi:10.7503/cjcu20170192

Abstract

Abstract:

We designed a new NO_x storage and reduction(NSR) CuO/K₂CO₃/MgAl₂O₄ catalyst operating at high temperature. The effect of potassium loading on the NO_x storage and reduction performance of the catalyst was studied. In the catalyst, the K₂CO₃ exists as highly dispersed K₂CO₃ and bulk K₂CO₃. In the lean-burn period, the nitrates formed on the bulk K₂CO₃ have high thermal stability at high operating temperature, while the thermal stability of the nitrates formed on the highly dispersed K₂CO₃ is low. When the K loading is low, the K₂CO₃ mainly exists as highly dispersed K₂CO₃, the limited NO_x storage capacity and the low thermal stability of the nitrates result in the low NSR activity at high temperature. While too much K₂CO₃ loaded on the catalyst can decrease the redox ability of CuO by covering it, which will decrease the NSR activity of the catalysts. When the K loading is 10%, the best NSR activity is obtained with the highest NO_x reduction percentage of 99. 9% at 450 ℃. Therefore, the CuO/K₂CO₃/MgAl₂O₄ catalyst is a promising high-temperature NSR catalyst.

Key words: High temperature, Non-noble metal, Potassium loading, Thermal stability, CuO/K₂CO₃/MgAl₂O₄ catalyst, NO_x storage and reduction

CLC Number:

O643

TrendMD:

LIU Yaoyao, DING Tong, ZHAO Dongyue, GAO Zhongnan, GUO Lihong, TIAN Ye, LI Xingang. Effect of Potassium Loading on the NO_x Storage and Reduction Performance of the CuO/K₂CO₃/MgAl₂O₄Catalyst at High Temperature^†[J]. Chem. J. Chinese Universities, 2017, 38(11): 2006.

Figures/Tables 12

Fig.1 Isothermal NOx storage curves of the CuO/K2CO3/MgAl2O4 catalysts with different K loadingsa. CuO/0K2CO3/MgAl2O4; b. CuO/5%K2CO3/MgAl2O4; c. CuO/10%K2CO3/MgAl2O4; d. CuO/20%K2CO3/MgAl2O4.

Table 1 NRP, NSC and NO conversion of the catalysts*

Catalyst	NRP(%)	NSC(mmol·g^-1)	NO conversion(%)
CuO/0K₂CO₃/MgAl₂O₄	57.9	0.19	33.4
CuO/5%K₂CO₃/MgAl₂O₄	68.2	0.38	33.9
CuO/10%K₂CO₃/MgAl₂O₄	99.9	1.56	33.7
CuO/20%K₂CO₃/MgAl₂O₄	98.4	1.64	33.2

Fig.2 NOx concentration curves during the lean/rich cycles(A) CuO/0K2CO3/MgAl2O4; (B) CuO/5%K2CO3/MgAl2O4; (C) CuO/10%K2CO3/MgAl2O4; (D) CuO/20%K2CO3/MgAl2O4.

Table 2 BET specific surface area(SBET), pore volume(Vp), pore diameter(dp) and Cu/K molar ratio of the fresh catalysts

Catalyst	$S BET a$ /(m²·g^-1)	$V p a$ /(cm³·g^-1)	$d p a$ /nm	Cu/K molar ratio^b
MgAl₂O₄	147.1	0.5	9.3
CuO/0K₂CO₃/MgAl₂O₄	125.6	0.5	9.6
CuO/5%K₂CO₃/MgAl₂O₄	110.3	0.4	9.5	0.35
CuO/10%K₂CO₃/MgAl₂O₄	77.4	0.3	9.3	0.29
CuO/20%K₂CO₃/MgAl₂O₄	49.4	0.2	9.1	0.19

Table 2 BET specific surface area(SBET), pore volume(Vp), pore diameter(dp) and Cu/K molar ratio of the fresh catalysts

Catalyst	$S BET a$ /(m²·g^-1)	$V p a$ /(cm³·g^-1)	$d p a$ /nm	Cu/K molar ratio^b
MgAl₂O₄	147.1	0.5	9.3
CuO/0K₂CO₃/MgAl₂O₄	125.6	0.5	9.6
CuO/5%K₂CO₃/MgAl₂O₄	110.3	0.4	9.5	0.35
CuO/10%K₂CO₃/MgAl₂O₄	77.4	0.3	9.3	0.29
CuO/20%K₂CO₃/MgAl₂O₄	49.4	0.2	9.1	0.19

Fig.3 XRD patterns of the fresh catalystsa. MgAl2O4; b. CuO/0K2CO3/MgAl2O4; c. CuO/5%K2CO3/MgAl2O4; d. CuO/10%K2CO3/MgAl2O4; e. CuO/20%K2CO3/MgAl2O4.

Fig.4 XRD patterns of the catalysts after NOx storage reactiona. CuO/0K2CO3/MgAl2O4; b. CuO/5%K2CO3/MgAl2O4; c. CuO/10%K2CO3/MgAl2O4; d. CuO/20%K2CO3/MgAl2O4.

Fig.5 XPS spectra of Cu2p(A) and K2p(B) of the fresh catalystsa. CuO/0K2CO3/MgAl2O4; b. CuO/5%K2CO3/MgAl2O4; c. CuO/10%K2CO3/MgAl2O4; d. CuO/20%K2CO3/MgAl2O4.

Fig.6 H2-TPR profiles of the fresh catalystsa. CuO/0K2CO3/MgAl2O4; b. CuO/5%K2CO3/MgAl2O4; c. CuO/10%K2CO3/MgAl2O4; d. CuO/20%K2CO3/MgAl2O4.

Fig.7 FTIR spectra of the samplesa. MgAl2O4; b. K2CO3; c. CuO/0K2CO3/MgAl2O4;d. CuO/5%K2CO3/MgAl2O4; e. CuO/10%K2CO3/MgAl2O4; f. CuO/20%K2CO3/MgAl2O4.

Fig.8 FTIR spectra of the catalysts after NOx storage reactiona. CuO/0K2CO3/MgAl2O4; b. CuO/5%K2CO3/MgAl2O4; c. CuO/10%K2CO3/MgAl2O4; d. CuO/20%K2CO3/MgAl2O4.

Fig.9 CO2-TPD profiles of the fresh catalysts a. CuO/5%K2CO3/MgAl2O4;b. CuO/10%K2CO3/MgAl2O4;c. CuO/20%K2CO3/MgAl2O4.

Fig.10 NOx-TPD profiles of the catalysts with different K loadings after NOx storagea. MgAl2O4; b. CuO/0K2CO3/MgAl2O4; c. CuO/5%K2CO3/MgAl2O4; d. CuO/10%K2CO3/MgAl2O4; e. CuO/20%K2CO3/MgAl2O4.

References 34

[1]	Kaspar J., Fornasiero P., Hickey N., Chem. J. Chinese Universities,2010, 31(4), 419-449
[2]	Kreuzer T., Lox E. S., Lindner D., Leyrer J., Chem. J. Chinese Universities,2010, 31(1-4), 17-27
[3]	Alkemade U. G., Schumann B., Chem. J. Chinese Universities,2010, 31(26), 2291-2296
[4]	Roy S., Baiker A., Chem. Rev., 2009, 109(9), 4054-4091
[5]	Koebel M., Elsener M., Kleemann M., Chem. J. Chinese Universities,2010, 31(3/4), 335-345
[6]	Gabrielsson P. L. T., Top. Catal., 2004, 28(1), 177-184
[7]	Sun X. L., He H., Su G. C., Yan J. F., Song L. Y., Qiu W. G., Chem. J. Chinese Universities,2010, 31(5), 814-822
	(孙向丽, 何洪, 苏垚超, 闫京芳, 宋丽云, 邱文革. 高等学校化学学报, 2017, 38(5), 814-822)
[8]	Shinjoh H., Takahashi N., Yokota K., Sugiura M., Appl. Catal. B-Environ., 1998, 15(3/4), 189-201
[9]	Sedlmair C., Seshan K., Jentys A., Lercher J., J. Catal., 2003, 214(2), 308-316
[10]	Takahashi N., Shinjoh H., Iijima T., Suzuki T., Yamazaki K., Yokota K., Suzuki H., Miyoshi N., Matsumoto S., Tanizawa T., Chem. J. Chinese Universities,2010, 31(1/2), 63-69
[11]	Takeuchi M., Matsumoto S. I., Top. Catal., 2004, 28(1), 151-156
[12]	Lietti L., Forzatti P., Nova I., Tronconi E., J. Catal., 2001, 204(17), 175-191
[13]	Kwak J. H., Kim D. H., Szanyi J., Cho S. J., Peden C. H. F., Top. Catal., 2012, 55(1), 70-77
[14]	Hatanaka M., Takahashi N., Tanabe T., Nagai Y., Suda A., Shinjoh H., J. Catal., 2009, 266(2), 182-190
[15]	Tanabe T., Nagai Y., Dohmae K., Sobukawa H., Shinjoh H., J. Catal., 2008, 257(1), 117-124
[16]	Luo J. Y., Gao F., Kim D. H., Peden C. H. F., Chem. J. Chinese Universities,2010, 31(4), 164-172
[17]	Zhang Y. X., Meng M., Dai F. F., Ding T., You R., Chem. J. Chinese Universities,2010, 31(45), 23691-23700
[18]	Takahashi N., Matsunaga S. I., Tanaka T., Sobukawa H., Shinjoh H., Appl. Catal. B-Environ., 2007, 77(1/2), 73-78
[19]	Luo J. Y., Gao F., Karim A. M., Xu P. H., Browning N. D., Peden C. H., ACS Catal., 2015, 5(8), 4680-4689
[20]	You R., Zhang Y. X., Liu D. S., Meng M., Zheng L. R., Zhang J., Hu T. D., Chem. J. Chinese Universities,2010, 31(44), 25403-25420
[21]	Li X. G., Dong Y. H., Xian H., Hernández W. Y., Meng M., Zo H. H., Ma A. J., Zhang T. Y., Jiang Z., Tsubaki N., Energy Environ. Sci., 2011, 4(9), 3351-3354
[22]	Lin T., Xu H. D., Li W., Zhang Q. L., Gong M. C., Chen Y. Q., Chem. J. Chinese Universities,2010, 31(11), 2240-2246
	(林涛, 徐海迪, 李伟, 张秋林, 龚茂初, 陈耀强. 高等学校化学学报, 2009, 30(11), 2240-2246)
[23]	Liu J. D., Huang Z. G., Li Z., Guo Q. Q., Li Q. Y., Chem. J. Chinese Universities,2010, 31(3), 589-595
	(刘建东, 黄张根, 李哲, 郭倩倩, 李巧艳. 高等学校化学学报, 2014, 35(3), 589-595)
[24]	Zhang Y. X., You R., Liu D. S., Liu C., Li X. G., Tian Y., Zheng J., Zhang S., Huang Y. Y., Zha Y. Q., Appl. Surf. Sci., 2015, 357, 2260-2276
[25]	Fan F. Q., Meng M., Tian Y., Zheng L. R., Zhang J., Hu T. D., Acta Phys. Chim. Sin., 2015, 31(9), 1761-1770
	(范丰奇, 孟明, 田野, 郑黎荣, 张静, 胡天斗. 物理化学学报, 2015, 31(9), 1761-1770)
[26]	Wang Q., Chung J. S., Appl. Catal. A-Gen., 2009, 358(1), 59-64
[27]	Ma A. J., Wang S. Z., Liu C., Xian H., Ding Q., Li X. G., Meng M., Tan Y. S., Tsubaki N., Zhang J., Appl. Catal. B-Environ., 2014, 146(5), 24-34
[28]	Avgouropoulos G., Ioannide T., Appl. Catal. A-Gen., 2003, 244(1), 155-167
[29]	Li R., Yu L. M., Yan X. F., Jiang T., Chem. J. Chinese Universities,2010, 31(2), 267-274
	(李如, 于良民, 闫雪峰, 江涛. 高等学校化学学报, 2017, 38(2), 267-274)
[30]	Liu N., Wang J. Q., Chen B. H., Li. Y. X., Zhang. R. D., Chem. J. Chinese Universities,2010, 31(10), 1817-1825
	(刘宁, 王继琼, 陈标华, 李英霞, 张润铎.高等学校化学学报, 2016, 37(10), 1817-1825)
[31]	Li X., Li Y. J., Li M., Tang N. M., Li. Z. Q., Han Z. Y., Chem. J. Chinese Universities,2010, 31(12), 2246-2252
	(林晓, 李佑稷, 李铭, 唐宁梅, 李紫琴, 韩志英. 高等学校化学学报, 2016, 37(12), 2246-2252)
[32]	Zhang G. Q., Zheng H. Y., He Z. Q., Li Y. Z., Chem. J. Chinese Universities,2010, 31(7), 1380-1389
	(张国强, 郑华艳, 郝志强, 李摇忠. 高等学校化学学报, 2016, 37(7), 1380-1389)
[33]	Iranmahboob J., Hill. D., Toghiani H., Appl. Surf. Sci., 2001, 185, 72-78
[34]	Toops T. J., Smith D. B., Partridge W. P., Appl. Catal. B-Environ., 2005, 58(3/4), 245-254

Effect of Potassium Loading on the NO_x Storage and Reduction Performance of the CuO/K₂CO₃/MgAl₂O₄Catalyst at High Temperature^†

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