Er掺杂对CeO2(ZrO2)/TiO2催化剂脱硝性能的影响

doi:10.1016/S1872-2067(16)62450-6

催化学报 ›› 2016, Vol. 37 ›› Issue (9): 1521-1529.DOI: 10.1016/S1872-2067(16)62450-6

Er掺杂对CeO₂(ZrO₂)/TiO₂催化剂脱硝性能的影响

金奇杰^a, 沈岳松^a, 祝社民^a, 李喜红^b, 胡敏^b

a. 江苏先进无机功能复合材料协同创新中心;南京工业大学材料科学与工程学院, 江苏南京 210009;
b. 山东天璨环保科技有限公司, 山东淄博 255086

收稿日期:2016-04-05 修回日期:2016-04-27 出版日期:2016-09-21 发布日期:2016-09-21
通讯作者: Yuesong Shen, Shemin Zhu
基金资助:
国家自然科学基金（51272105）；江苏省科技支撑计划（BE2013718）；江苏省环保科研支撑计划（2013006）；江苏高校优势学科建设工程资助项目（PAPD）.

Promotional effects of Er incorporation in CeO₂(ZrO₂)/TiO₂ for selective catalytic reduction of NO by NH₃

Qijie Jin^a, Yuesong Shen^a, Shemin Zhu^a, Xihong Li^b, Min Hu^b

a. Jiangsu Collaborative Innovation Center for Advanced Inorganic Function Composites, Jiangsu National Synergetic Innovation Center for Advanced Materials(SICAM), College of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009, Jiangsu, China;
b. Shandong Gemsky Environmental Technology Co., Zibo 255086, Shandong, China

Received:2016-04-05 Revised:2016-04-27 Online:2016-09-21 Published:2016-09-21
Contact: Yuesong Shen, Shemin Zhu
Supported by:
This work was supported by the National Natural Science Foundation of China(51272105), Jiangsu Provincial Science and Technology Supporting Program(BE2013718), Research Subject of Environmental Protection Department of Jiangsu Province of China(2013006), and Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).

摘要/Abstract

摘要：

氮氧化物（NO_x）是大气污染的主要因素之一，对其排放的治理成为较为迫切的需求.氨气选择性催化还原法（NH₃-SCR）是目前减少NO_x排放中应用最为广泛的技术.目前，商业SCR催化剂主要是V₂O₅（WO₃，MO₃）/TiO₂，但其具有活性温度窗口窄、N₂选择性低和对环境影响大等缺点.因此，新型的催化活性高且活性温度窗口宽的环境友好催化剂成为脱硝催化剂的研究热点.CeO₂因其独特的氧化还原性能和优异的储释氧能力在催化领域具有广泛应用，在NH₃-SCR中也研发出较多类型的铈基催化剂.我们课题组前期研发了具有优异脱硝性能的CeO₂（ZrO₂）/TiO₂催化剂，为拓展其应用范围，需要进行更深入的研究.理论上，Ti⁴⁺，Ce⁴⁺以及Zr⁴⁺离子的价态均高于Er³⁺，且离子半径相近.换言之，Er₂O₃能够与TiO₂以及CeO₂产生缺陷反应增大催化剂的缺陷浓度，进而提高催化剂的催化活性.本文以溶胶-凝胶法制备了一系列Er掺杂CeO₂（ZrO₂）/TiO₂催化剂，测试了样品的NH₃-SCR催化活性和N₂选择性，并且在320℃下连续24 h测试了水蒸气、SO₂以及两者混合作用对催化剂活性的影响.使用X射线衍射（XRD）、N₂等温吸附-脱附（N₂-BET）、NH₃程序升温脱附（NH₃-TPD）、H₂程序升温还原（H₂-TPR）、光致发光光谱（PL）、电子顺磁共振（EPR）以及X射线光电子能谱（XPS）对催化剂进行了表征.XRD结果显示，Er掺杂后催化剂的结晶程度降低，且图谱中没有出现明显的Er₂O₃衍射峰，即Er在催化剂上有较好的分散度且掺杂抑制了催化剂的晶化.NH₃-TPD和H₂-TPR结果表明，Er掺杂降低了酸强且提高了储释氧能力，催化剂的氧化还原能力则有所减弱.PL和EPR测试结果显示，掺杂后的催化剂氧空位浓度和Ti³⁺浓度有所增加，与前期理论设计一致.XPS测试结果表明，掺入Er后催化剂的化学吸附氧含量和Ti³⁺浓度增加，Ce³⁺浓度基本不变，推测是CeO₂（ZrO₂）/TiO₂催化剂中掺入的Er主要与载体TiO₂，而不是与活性组分CeO₂或助剂ZrO₂产生缺陷反应的结果.CeO₂（ZrO₂）/TiO₂催化剂最高活性为94.28%，其活性温度窗口为230-390℃，掺入Er（Er：Ce=0.10：1）后，催化剂的整体活性尤其是350℃以下的催化活性具有明显提升，最高活性达到98.85%，活性温度窗口也拓展为220-395℃.单独的水蒸气对催化活性影响很小，SO₂会部分降低催化剂活性，而当两者混合作用时，催化剂活性下降最为显著，且Er掺杂后CeO₂（ZrO₂）/TiO₂催化剂的抗中毒能力有所增强.Er掺杂CeO₂（ZrO₂）/TiO₂催化剂显示出较好的抗硫抗水中毒能力以及较高的NH₃-SCR催化活性和N₂选择性，应该是一种具有应用前景的SCR催化剂.Er掺杂降低了催化剂的酸强，抑制了TiO₂和铈锆固溶体的晶化，提高了Ti³⁺和氧空位浓度并增强了储释氧能力，是CeO₂（ZrO₂）/TiO₂催化剂活性提高的主要原因.

关键词: CeO₂(ZrO₂)/TiO₂, 铒掺杂, 选择性催化还原, 氮氧化物, 催化性能

Abstract:

A series CeO₂(ZrO₂)/TiO₂ catalysts were modified with Er using a sol-gel method. The catalytic activity of the obtained catalysts in the selective catalytic reduction(SCR) of NO with NH₃ was investigated to determine the appropriate Er dosage. The catalysts were characterized using X-ray diffraction, N₂ adsorption, NH₃ temperature-programmed desorption, H₂ temperature-programmed reduction, photoluminescence spectroscopy, electron paramagnetic resonance spectroscopy, and X-ray photoelectron spectroscopy. The results showed that the optimum Er/Ce molar ratio was 0.10; this catalyst had excellent resistance to catalyst poisoning caused by vapor and sulfur and gave more than 90% NO conversion at 220-395℃ and a gas hourly space velocity of 71 400 h^-1. Er incorporation increased the Ti³⁺ concentrations, oxygen storage capacities, and oxygen vacancy concentrations of the catalysts, resulting in excellent catalytic performance. Er incorporation also decreased the acid strength and inhibited growth of TiO₂ and CeO₂ crystal particles, which increased the catalytic activity. The results show that high oxygen vacancy concentrations and oxygen storage capacities, large amounts of Ti³⁺, and low acid strengths give excellent SCR activity.

Key words: CeO₂(ZrO₂)/TiO₂, Erbium incorporation, Selective catalytic reduction, Nitrogen oxide, Catalytic performance

金奇杰, 沈岳松, 祝社民, 李喜红, 胡敏. Er掺杂对CeO₂(ZrO₂)/TiO₂催化剂脱硝性能的影响[J]. 催化学报, 2016, 37(9): 1521-1529.

Qijie Jin, Yuesong Shen, Shemin Zhu, Xihong Li, Min Hu. Promotional effects of Er incorporation in CeO₂(ZrO₂)/TiO₂ for selective catalytic reduction of NO by NH₃[J]. Chinese Journal of Catalysis, 2016, 37(9): 1521-1529.

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Er掺杂对CeO₂(ZrO₂)/TiO₂催化剂脱硝性能的影响

Promotional effects of Er incorporation in CeO₂(ZrO₂)/TiO₂ for selective catalytic reduction of NO by NH₃

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