柴油机尾气中的碱性无机污染物引起Cu-SAPO-18脱硝催化剂的化学失活

引用本文: 明淑君, 庞磊, 范驰, 郭文, 董亚浩, 刘鹏, 陈真, 李涛. 柴油机尾气中的碱性无机污染物引起Cu-SAPO-18脱硝催化剂的化学失活[J]. 催化学报, 2019, 40(4): 590-599. doi: S1872-2067(19)63312-7 shu

Citation: Shujun Ming, Lei Pang, Chi Fan, Wen Guo, Yahao Dong, Peng Liu, Zhen Chen, Tao Li. Chemical deactivation of Cu-SAPO-18 deNO_x catalyst caused by basic inorganic contaminants in diesel exhaust[J]. Chinese Journal of Catalysis, 2019, 40(4): 590-599. doi: S1872-2067(19)63312-7 shu

柴油机尾气中的碱性无机污染物引起Cu-SAPO-18脱硝催化剂的化学失活

明淑君 ^a, ,
庞磊 ^b, ,
范驰 ^a, ,
郭文 ^a, ,
董亚浩 ^a, ,
刘鹏 ^a, ,
陈真 ^a, ,
李涛 ^a,

a 华中科技大学化学与化工学院, 能量转换存储材料化学教育部重点实验室, 材料化学与服役失效湖北省重点实验室, 湖北武汉 430074;
b 武汉东风汽车研发中心, 湖北武汉 430056
基金项目:
国家自然科学基金（21473064）.

摘要: 选择性催化还原NO_x（NH₃-SCR）已是柴油机尾气处理系统中有效的NO_x减排技术.铜基分子筛催化剂作为潜在的NH₃-SCR催化剂已被广泛研究，其中具有AEI结构的Cu-SAPO-18分子筛表现出优异的脱硝活性和水热稳定性，成为柴油机尾气后处理系统潜在的替代品.然而在实际的后处理应用中，生物柴油污染物、发动机润滑剂和燃料添加剂中的一些无机组分（K，Na，S，P，Ca和Mg等）可逐渐聚集在催化剂表面，导致催化剂孔道堵塞和活性位点丢失，最终导致SCR催化剂失活.由于碱金属和碱土金属在柴油衍生物中含量较高，因而其对SCR催化剂的影响引起了人们更多的关注.本文采用浸渍法制备了掺杂不同含量碱性无机污染物（K，Na，Ca和Mg）的Cu-SAPO-18催化剂，以阐明这些污染物对Cu-SAPO-18结构、酸性位点和铜物种的影响.
XRD和氮吸附实验结果表明，低含量污染物的掺入造成催化剂孔道堵塞和比表面积下降，而高含量污染物引入导致催化剂部分结构被破坏，其中高含量Na的引入造成催化剂结构破坏最为严重.H₂-TPR和EPR结果表明，污染物引入Cu-SAPO-18后，催化剂的Cu²⁺数目减少，这是由于Cu²⁺被K⁺，Na⁺，Ca²⁺和Mg²⁺取代造成的.被取代的Cu²⁺由于无法位于离子交换位点上会在煅烧过程中转变成CuO和CuAl₂O₄，CuO的产生会造成催化剂孔道堵塞甚至部分骨架结构坍塌.另外，NH₃-TPD结果表明，与新鲜催化剂相比，被污染的Cu-SAPO-18催化剂总酸性位点减少，这是由于H⁺和Cu²⁺被K⁺，Na⁺，Ca²⁺和Mg²⁺取代造成Brönsted酸和Lewis酸减少造成的.催化剂比表面积的降低、Cu²⁺数目以及酸含量的减少最终造成催化剂失活，且催化剂失活程度随无机污染物含量的增加而增大.但不同无机组分造成催化剂的失活程度不同，其中K，Na，Ca和Mg造成Cu-SAPO-18催化剂失活程度为K > Na > Ca > Mg.此外，K，Na，Ca和Mg造成Cu-SAPO-18催化剂比表面积、Cu²⁺含量以及酸含量的减少程度分别为Na > K > Ca > Mg，Na > K > Mg > Ca和K > Na > Ca > Mg.其中酸含量下降程度与催化剂失活程度一致，表明在某种程度上，酸含量对催化剂NH₃-SCR活性的影响高于催化剂结构和Cu²⁺对活性的影响.最后，我们还通过NH₃-SCR动力学测试研究了K，Na，Ca和Mg对Cu-SAPO-18催化NH₃-SCR反应机理的影响，结果显示新鲜催化剂和被污染催化剂具有相近的活化能，表明无机污染物对Cu-SAPO-18催化NH₃-SCR反应机理没有影响.

关键词:

English

Chemical deactivation of Cu-SAPO-18 deNO_x catalyst caused by basic inorganic contaminants in diesel exhaust

Shujun Ming ^a, ,
Lei Pang ^b, ,
Chi Fan ^a, ,
Wen Guo ^a, ,
Yahao Dong ^a, ,
Peng Liu ^a, ,
Zhen Chen ^a, ,
Tao Li ^a,

a Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China;
b DongFeng Trucks R & D Center, Wuhan 430056, Hubei, China
Received Date: 19 November 2018
Revised Date: 11 January 2019
Fund Project:
This work was supported by the National Natural Science Foundation of China (21473064).

Abstract: Contaminants (K, Na, Ca, and Mg) were introduced into Cu-SAPO-18 via incipient wetness impregnation to investigate their effect on the selective catalytic reduction of NO_x with NH₃ (NH₃-SCR) over Cu-SAPO-18. After the introduction of contaminants into Cu-SAPO-18, the quantity of acidic sites and Cu²⁺ species in catalyst decreases owing to the replacement of H⁺ and Cu²⁺ by K⁺, Na⁺, Ca²⁺, and Mg²⁺. Furthermore, the loss of isolated Cu²⁺ induces the generation of CuO and CuAl₂O₄-like phases, which causes further loss in the Brunauer-Emmett-Teller surface area of the catalyst. Consequently, the deNO_x performance of the contaminated Cu-SAPO-18 catalysts drops. Such decline in NH₃-SCR performance becomes more pronounced by increasing the contaminant contents from 0.5 to 1.0 mmol/g_catal. In addition, the deactivation influence of the contaminants on Cu-SAPO-18 is presented in the order of K > Na > Ca > Mg, which is consistent with the order of reduction of acidic sites. To a certain degree, the effect of the acidic sites on the deactivation of Cu-SAPO-18 might be more significant than that of isolated Cu²⁺ and the catalyst framework. Moreover, kinetic analysis of NH₃-SCR was conducted, and the results indicate that there is no influence of contaminants on the NH₃-SCR mechanism.

Key words:

Cu-SAPO-18 catalyst
/ Basic inorganic contaminant
/ Selective catalytic reduction of NO_x with NH₃
/ Acidic site
/ Isolated Cu²⁺

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沈阳化工大学材料科学与工程学院沈阳 110142

柴油机尾气中的碱性无机污染物引起Cu-SAPO-18脱硝催化剂的化学失活

English

Chemical deactivation of Cu-SAPO-18 deNO_x catalyst caused by basic inorganic contaminants in diesel exhaust

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中国化学会秘书处

柴油机尾气中的碱性无机污染物引起Cu-SAPO-18脱硝催化剂的化学失活

English

Chemical deactivation of Cu-SAPO-18 deNOx catalyst caused by basic inorganic contaminants in diesel exhaust

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？

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通讯作者: 陈斌, bchen63@163.com

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Chemical deactivation of Cu-SAPO-18 deNO_x catalyst caused by basic inorganic contaminants in diesel exhaust

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