氨法选择性还原氮氧化物V2O5/TiO2-PILC催化剂的抗硫性能

引用本文: 臧思淼, 张桂臻, 邱文革, 宋丽云, 张然, 何洪. 氨法选择性还原氮氧化物V₂O₅/TiO₂-PILC催化剂的抗硫性能[J]. 催化学报, 2016, 37(6): 888-897. doi: 10.1016/S1872-2067(15)61083-X shu

Citation: Simiao Zang, Guizhen Zhang, Wenge Qiu, Liyun Song, Ran Zhang, Hong He. Resistance to SO₂ poisoning of V₂O₅/TiO₂-PILC catalyst for the selective catalytic reduction of NO by NH₃[J]. Chinese Journal of Catalysis, 2016, 37(6): 888-897. doi: 10.1016/S1872-2067(15)61083-X shu

氨法选择性还原氮氧化物V₂O₅/TiO₂-PILC催化剂的抗硫性能

北京工业大学环境与能源工程学院化学化工系, 区域大气污染防治北京市重点实验室, 绿色催化与分离北京市重点实验室, 北京 100124
基金项目:
国家自然科学基金(21277009, 21577005).

摘要: 选择性催化还原 (SCR) 是目前去除氮氧化物最有效的方法之一. V₂O₅/TiO₂催化剂被广泛应用于氨法选择性还原氮氧化物 (NH₃-SCR) 反应, 但该催化剂存在工作温度高 (300-400 ^oC)及 SO₂氧化率高引起设备腐蚀和管路堵塞等问题, 开发低温 SCR 催化剂具有重要意义. 过渡金属氧化物 (如 Fe₂O₃, MnO_x和 CuO 等) 催化剂用于低温SCR先后见诸文献报道, 但这些催化剂在 SO₂和 H₂O 存在下易失活. 近年来柱撑黏土 (PILC) 引起科学家广泛关注, Yang 等首次将 V₂O₅/TiO₂-PILC 催化剂应用于 NH₃-SCR 反应, 发现其催化活性高于传统 V₂O₅/TiO₂催化剂. 柱撑黏土基催化剂在 NH₃-SCR 反应中也显示出良好抗硫性能, 但 V₂O₅/TiO₂-PILC 催化剂的抗硫机理至今尚未见深入研究. 因此我们制备了一系列 V₂O₅/TiO₂-PILC 催化剂, 采用原位漫反射红外等方法详细研究了其抗硫性能较好的原因.
首先采用离子交换法制备出 TiO₂-PILC 载体, 之后采用浸渍法制备了不同钒含量 (质量分数x/% = 0, 3, 4, 5) 的 xV₂O₅/TiO₂-PILC 催化剂. 同时, 制备了传统 V₂O₅/TiO₂和 V₂O₅-MoO₃/TiO₂催化剂作为对比. 活性评价结果显示, 4V/TiO₂-PILC 催化剂具有最高的催化活性, 其催化性能与传统钒钛催化剂相当. 在 160 ^oC 时, NO 转化率可达 80% 以上. 同时, 4V/TiO₂-PILC 催化剂还具有较宽的反应温度窗口, 在 260-500 ^oC 范围内, NO 转化率保持在 90% 以上. 向反应体系中加入 0.05% SO₂和 10% H₂O 后, 在低温 (160 ^oC 以下) 时所有催化剂的反应活性都有一定提高, 可能是由于 SO₂的加入提高了催化剂的表面酸性. 继续升高温度, 4V/TiO₂和 4V6Mo/TiO₂催化剂活性均明显下降, 而 4V/TiO₂-PILC 催化剂的活性则未出现明显下降. 原位漫反射红外光谱结果显示, SO₂在三种催化剂表面的吸附以表面硫酸盐或亚硫酸盐物种以及离子态 SO₄^2-物种形式存在, 而在 4V/TiO₂-PILC 催化剂表面离子态 SO₄^2-物种的量最少. X射线光电子能谱及 O₂程序升温脱附结果显示, 在 4V/TiO₂-PILC 催化剂上, 表面吸附氧 (O_ads) 的量最少. 综合上述分析可以得出, 在 SO₂气氛下, 离子态 SO₄^2-物种在 SCR 催化剂表面的累积可能是导致其失活的主要原因, 而离子态 SO₄^2-物种的形成可能与催化剂表面吸附氧的量有关.

关键词:

English

Resistance to SO₂ poisoning of V₂O₅/TiO₂-PILC catalyst for the selective catalytic reduction of NO by NH₃

Key Laboratory of Beijing on Regional Air Pollution Control; Beijing Key Laboratory for Green Catalysis and Separation; Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, China
Received Date: 29 January 2016
Revised Date: 05 March 2016
Fund Project:
This work was supported by the National Natural Science Foundation of China (21277009, 21577005).

Abstract: A titania pillared interlayered clay (Ti-PILC) supported vanadia catalyst (V₂O₅/TiO₂-PILC) was prepared by wet impregnation for the selective catalytic reduction (SCR) of NO with ammonia. Compared to the traditional V₂O₅/TiO₂ and V₂O₅-MoO₃/TiO₂ catalysts, the V₂O₅/TiO₂-PILC catalyst exhibited a higher activity and better SO₂ and H₂O resistance in the NH₃-SCR reaction. Characterization using TPD, in situ DRIFT and XPS showed that surface sulfate and/or sulfite species and ionic SO₄²^-species were formed on the catalyst in the presence of SO₂. The ionic SO₄²^-species on the catalyst surface was one reason for deactivation of the catalyst in SCR. The formation of the ionic SO₄²^- species was correlated with the amount of surface adsorbed oxygen species. Less adsorbed oxygen species gave less ionic SO₄²^- species on the catalyst.

Key words:

Selective catalytic reduction
/ TiO₂-pillared clay
/ Nitrogen oxide
/ Vanadia catalyst
/ In situ diffuse reflectance infrared Fourier transform spectroscopy

1. [1] P. Forzatti, Catal. Today, 2000, 62, 51-65.
2. [2] W. Müller, H. Ölschlegel, A. Schäfer, N. Hakim, K. Binder, SAE, 2003, 2003-01-2304.
3. [3] G. Busca, L. Lietti, G. Ramis, F. Berti, Appl. Catal. B, 1998, 18, 1-36.
4. [4] P. Granger, V. I. Parvulescu, Chem. Rev., 2011, 111, 3155-3207.
5. [5] S. Roy, M. S. Hegde, G. Madras, Appl. Energy, 2009, 86, 2283-2297.
6. [6] J. L. Valverde, A. de Lucas, P. Sánchez, F. Dorado, A. Romero, Appl. Catal. B, 2003, 43, 43-56.
7. [7] G. S. Qi, R. T. Yang, R. Chang, Catal. Lett., 2003, 87, 67-71.
8. [8] S. Roy, B. Viswanath, M. S. Hegde, G. Madras, J. Phys. Chem. C, 2008, 112, 6002-6012.
9. [9] B. C. Huang, R. Huang, D. J. Jin, D. Q. Ye, Catal. Today, 2007, 126, 279-283.
10. [10] R. Q. Long, R. T. Yang, R. Chang, Chem. Commun., 2002, 452-453.
11. [11] F. D. Liu, H. He, C. B. Zhang, Z. C. Feng, L. R. Zheng, Y. N. Xie, T. D. Hu, Appl. Catal. B, 2010, 96, 408-420.
12. [12] G. S. Qi, R. T. Yang, J. Catal., 2003, 217, 434-441.
13. [13] X. L. Tang, J. M. Hao, H. H. Yi, J. H. Li, Catal. Today, 2007, 126, 406-411.
14. [14] S. M. Lee, K. H. Park, S. C. Hong, Chem. Eng. J., 2012, 195-196, 323-331.
15. [15] M. Ouzzine, G. A. Cifredo, J. M. Gatica, S. Harti, T. Chafik, H. Vidal, Appl. Catal. A, 2008, 342, 150-158.
16. [16] Y. L. Wang, Z. Y. Liu, L. Zhan, Z. G. Huang, Q. Y. Liu, J. R. Ma, Chem. Eng. Sci., 2004, 59, 5283-5290.
17. [17] E. Garcia-Bordejee, J. L. Pinilla, M. J. Lazaro, R. Moliner, J. L. G. Fierro, J. Catal., 2005, 233, 166-175.
18. [18] R. T. Yang, J. P. Chen, E. S. Kikkinides, L. S. Cheng, J. E. Cichanowicz, Ind. Eng. Chem. Res., 1992, 31, 1440-1445.
19. [19] J. P. Chen, M. C. Hausladen, R. T. Yang, J. Catal., 1995, 151, 135-146.
20. [20] L. S. Cheng, R. T. Yang, N. Chen, J. Catal., 1996, 164, 70-81.
21. [21] R. Q. Long, R. T. Yang, Appl. Catal. B, 2000, 24, 13-21.
22. [22] R. Q. Long, R. T. Yang, J. Catal., 2000, 190, 22-31.
23. [23] C. Orsenigo, L. Lietti, E. Tronconi, P. Forzatti, F. Bregani, Ind. Eng. Chem. Res., 1998, 37, 2350-2359.
24. [24] X. Y. Guo, C. Bartholomew, W. Hecker, L. L. Baxter, Appl. Catal. B, 2009, 92, 30-40.
25. [25] R. Q. Long, R. T. Yang, J. Catal., 1999, 186, 254-268.
26. [26] J. Sterte, Clays Clay Miner., 1986, 34, 658-664.
27. [27] N. N. Binitha, S. Sugunan, Microporous Mesoporous Mater., 2006, 93, 82-89.
28. [28] H. J. Chae, I. S. Nam, S. W. Ham, S. B. Hong, Appl. Catal. B, 2004, 53, 117-126.
29. [29] L. Chmielarz, P. Kustrowski, M. Zbroja, A. Rafalska-Lasocha, B. Dudek, R. Dziembaj, Appl. Catal. B, 2003, 45, 103-116.
30. [30] Y. X. Chen, Y. Jiang, W. Z. Li, R. C. Jin, S. Z. Tang, W. B. Hu, Catal. Today, 1999, 50, 39-47.
31. [31] S. T. Choo, S. D. Yim, I. S. Nam, S. W. Ham, J. B. Lee, Appl. Catal. B, 2003, 44, 237-252.
32. [32] S. J. Hug, J. Colloid Interface Sci., 1997, 188, 415-422.
33. [33] D. Peak, R. G. Ford, D. L. Sparks, J. Colloid Interface Sci., 1999, 218, 289-299.
34. [34] J. J. Murcia, M. C. Hidalgo, J. A. Navio, J. Arana, J. M. Dona-Rodriguez, Appl. Catal. B, 2013, 142-143, 205-213.
35. [35] A. Brückner, U. Bentrup, J. B. Stelzer, Z. Anorg. Allg. Chem., 2005, 631, 60-66.
36. [36] J. P. Dunn, P. R. Koppula, H. G. Stenger, I. E. Wachs, Appl. Catal. B, 1998, 19, 103-117.
37. [37] T. Luo, R. J. Gorte, Appl. Catal. B, 2004, 53, 77-85.
38. [38] W. Q. Xu, H. He, Y. B. Yu, J. Phys. Chem. C, 2009, 113, 4426-4432.
39. [39] C. Morterra, J. Chem. Soc., Faraday Trans. I, 1988, 84, 1617-1637.
40. [40] Yu. V. Belokopytov, K. M. Kholyavenko, S. V. Gerei, J. Catal., 1979, 60, 1-7.
41. [41] G. S. Qi, R.T. Yang, J. Phys. Chem. B, 2004, 108, 15738-15747.
42. [42] G. M. Underwood, T. M. Miller, V. H. Grassian, J. Phys. Chem. A, 1999, 103, 6184-6190.
43. [43] K. I. Hadjiivanov, Catal. Rev. Sci. Eng., 2000, 42, 71-144.
44. [44] H. Y. Huang, R. T. Yang, Langmuir, 2001, 17, 4997-5003.
45. [45] S. H. Xie, J. G. Deng, S. M. Zang, H. G. Yang, G. S. Guo, H. Arandiyan, H. X. Dai, J. Catal., 2015, 322, 38-48.
46. [46] W. P. Shan, F. D. Liu, H. He, X. Y. Shi, C. B. Zhang, Appl. Catal. B, 2012, 115-116, 100-106.
47. [47] X. L. Chu, Z. S. Lu, Z. X. Yang, D. W. Ma, Y. X. Zhang, S. S. Li, P. Y. Gao, Phys. Lett. A, 2014, 378, 659-666.
48. [48] L. Chen, J. H. Li, M. F. Ge, J. Phys. Chem. C, 2009, 113, 21177-21184.
49. [49] G. S. Wong, J. M. Vohs, Surf. Sci., 2002, 498, 266-274.
50. [50] S. H. Xie, J. G. Deng, Y. X. Liu, Z. H. Zhang, H. G. Yang, Y. Jiang, H. Arandiyanc, H. X. Dai, C. T. Au, Appl. Catal. A, 2015, 507, 82-90.
51. [51] W. Deng, Q. G. Dai, Y. J. Lao, B. B. Shi, X. Y. Wang, Appl. Catal. B, 2016, 181, 848-861.
52. [52] Y. L. Liu, S. Yang, Y. Lu, N. V. Podval, W. Chen, G. S. Zakharova, Appl. Surf. Sci., 2015, 359, 114-119.

扫一扫看文章

计量

PDF下载量: 0
文章访问数: 763
HTML全文浏览量: 161

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

氨法选择性还原氮氧化物V₂O₅/TiO₂-PILC催化剂的抗硫性能

English

Resistance to SO₂ poisoning of V₂O₅/TiO₂-PILC catalyst for the selective catalytic reduction of NO by NH₃

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处