Ho改性的Mn-Ce/TiO2催化剂低温脱硝性能的评价和表征

doi:10.1016/S1872-2067(18)63099-2

催化学报 ›› 2018, Vol. 39 ›› Issue (10): 1653-1663.DOI: 10.1016/S1872-2067(18)63099-2

Ho改性的Mn-Ce/TiO₂催化剂低温脱硝性能的评价和表征

李伟, 张成, 李鑫, 谭鹏, 周安鹂, 方庆艳, 陈刚

华中科技大学, 能源与动力工程学院, 煤燃烧国家重点实验室, 湖北武汉 430074

收稿日期:2018-04-04 修回日期:2018-05-08 出版日期:2018-10-18 发布日期:2018-08-03
通讯作者: 张成, 陈刚
基金资助:
国家重点研发计划重点专项（2018YFB0605105）.

Ho-modified Mn-Ce/TiO₂ for low-temperature SCR of NO_x with NH₃: Evaluation and characterization

Wei Li, Cheng Zhang, Xin Li, Peng Tan, Anli Zhou, Qingyan Fang, Gang Chen

State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China

Received:2018-04-04 Revised:2018-05-08 Online:2018-10-18 Published:2018-08-03
Contact: 10.1016/S1872-2067(18)63099-2
Supported by:
This work was supported by the National Key Research and Development Program of China (NO.2018YFB0605105);the technical support from the Analytical and Testing Center at the Huazhong University of Science and Technology is greatly appreciated.

摘要/Abstract

摘要：

作为引起酸雨、光化学烟雾、雾霾等大气污染问题的主要根源，氮氧化物（NO_x）的防治已成为亟待解决的问题。选择性催化还原技术作为最成熟有效的脱硝技术，目前已经被广泛应用于各燃煤电厂.低温脱硝催化剂具有优秀的低温活性，使得脱硝装置可以安放在脱硫装置和除尘装置下游，受到了学者广泛的研究.目前低温脱硝催化剂的研究主要是对催化剂进行改性以提高催化剂的性能，已有许多研究报道了Sn、Ni、Co、Zr、Cr、Ni等对催化剂的改性影响.Ho作为一种改性元素被应用于光催化领域，能提高TiO₂的光催化能力.但Ho应用于脱硝领域的研究鲜有报道，其氧化物具有酸性位点有助于脱硝反应，因此研究Ho对低温SCR催化剂的改性作用具有重要意义.
本文采用浸渍法制备Ho掺杂的Mn-Ce/TiO₂催化剂，研究了Ho的掺杂对于Mn-Ce/TiO₂催化剂低温脱硝性能的影响，同时还研究了烟气中的SO₂和H₂O对催化剂活性的影响，并利用XPS、XRD、H₂-TPR、NH₃-TPD等表征方法从物理性质和化学性质两方面对Ho改性的影响机理进行了研究.研究发现，Ho的掺杂能提高Mn-Ce/TiO₂催化剂的脱硝能力，有助于催化剂N₂选择性的提高.分析表明，Ho的掺杂有助于催化剂比表面积的提升，且能提高催化剂的酸性，有利于催化剂对NH₃的吸附，从而提高催化剂的性能.XPS表征结果表明Ho掺杂后的催化剂具有更高的化学吸附氧浓度和较高的Mn⁴⁺/Mn³⁺比例，使得脱硝反应更容易进行.改性后催化剂的抗水抗硫实验结果表明，Ho的掺杂能够提高催化剂的抗水抗硫性能.XRD结果表明，抗水抗硫实验后催化剂表面形成了硫酸铵盐，硫酸铵盐的形成会堵塞催化剂表面的活性位，限制脱硝反应的进行，从而影响催化剂的脱硝活性.同时，400℃下进行再生实验后的催化剂活性有所恢复，但是未能达到抗水抗硫实验前的活性，表明在抗水抗硫实验中催化剂表面形成了除硫酸铵盐以外的其他硫酸盐类.结合XPS和XRD表征结果，推断生成的盐类物质为硫酸锰和硫酸铈，从而导致再生后的催化剂的脱硝活性无法恢复到最初的活性水平.由此可以看出，硫酸盐的形成是催化剂在含硫气氛中失活的主要原因.

关键词: Mn-Ce-Ho/TiO₂, 低温选择性催化还原, 催化剂, 钬, 二氧化硫

Abstract:

Low-temperature selective catalytic reduction (SCR) of NO with NH₃ was tested over Ho-doped Mn-Ce/TiO₂ catalysts prepared by the impregnation method. The obtained catalysts with different Ho doping ratios were characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), temperature-programmed reduction (H₂-TPR), temperature-programmed desorption of NH₃ (NH₃-TPD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The catalytic activities were tested on a fixed bed. Their results indicated that the proper doping amount of Ho could effectively improve the low-temperature denitrification performance and the SO₂ resistance of Mn-Ce/TiO₂ catalyst. The catalyst with Ho/Ti of 0.1 presented excellent catalytic activity, with a conversion of more than 90% in the temperature window of 140-220℃. The characterization results showed that the improved SCR activity of the Mn-Ce/TiO₂ catalyst caused by Ho doping was due to the increase of the specific surface area, higher concentration of chemisorbed oxygen, higher surface Mn⁴⁺/Mn³⁺ ratio, and higher acidity. The SO₂ resistance test showed that the deactivating influence of SO₂ on the catalyst was irreversible. The XRD and XPS results showed that the main reason for the catalyst deactivation was sulfates that had formed on the catalyst surface and that Ho doping could inhibit the sulfation to some extent.

Key words: Mn-Ce-Ho/TiO₂, Low-temperature selective catalytic reduction, Catalyst, Holmium, SO₂

李伟, 张成, 李鑫, 谭鹏, 周安鹂, 方庆艳, 陈刚. Ho改性的Mn-Ce/TiO₂催化剂低温脱硝性能的评价和表征[J]. 催化学报, 2018, 39(10): 1653-1663.

Wei Li, Cheng Zhang, Xin Li, Peng Tan, Anli Zhou, Qingyan Fang, Gang Chen. Ho-modified Mn-Ce/TiO₂ for low-temperature SCR of NO_x with NH₃: Evaluation and characterization[J]. Chinese Journal of Catalysis, 2018, 39(10): 1653-1663.

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Ho改性的Mn-Ce/TiO₂催化剂低温脱硝性能的评价和表征

Ho-modified Mn-Ce/TiO₂ for low-temperature SCR of NO_x with NH₃: Evaluation and characterization

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