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中温商业SCR催化剂碱和碱土中毒特性研究

沈伯雄 卢凤菊 高兰君 岳时吉

沈伯雄, 卢凤菊, 高兰君, 岳时吉. 中温商业SCR催化剂碱和碱土中毒特性研究[J]. 燃料化学学报, 2016, 44(4): 500-506.
引用本文: 沈伯雄, 卢凤菊, 高兰君, 岳时吉. 中温商业SCR催化剂碱和碱土中毒特性研究[J]. 燃料化学学报, 2016, 44(4): 500-506.
SHEN Bo-xiong, LU feng-ju, GAO Lan-jun, YUE Shi-ji. Study on alkali and alkaline earths poisoning characteristics for a commercial SCR catalyst[J]. Journal of Fuel Chemistry and Technology, 2016, 44(4): 500-506.
Citation: SHEN Bo-xiong, LU feng-ju, GAO Lan-jun, YUE Shi-ji. Study on alkali and alkaline earths poisoning characteristics for a commercial SCR catalyst[J]. Journal of Fuel Chemistry and Technology, 2016, 44(4): 500-506.

中温商业SCR催化剂碱和碱土中毒特性研究

基金项目: 

基金国家自然科学基金项目 51541602

海外青年基金 51550110237

详细信息
  • 中图分类号: X511

Study on alkali and alkaline earths poisoning characteristics for a commercial SCR catalyst

More Information
  • 摘要: 在实验室条件下对选择性催化还原(SCR)商业催化剂的碱(K)和碱土(Ca)中毒进行了模拟,并采用液氮吸附、扫描电镜、能谱分析、NH3-程序升温脱附、H2-程序升温还原等方法对催化剂中毒前后的物理化学性质变化进行了表征。结果表明, K和Ca的中毒没有破坏商业中温SCR催化剂孔的基本结构,但K和Ca的中毒使催化剂的比表面积和孔容减小。K和Ca的中毒在一定程度上改变了催化剂表面钒的价态,导致了钒的还原能力减弱,同时降低催化剂表面化学吸附氧。钾中毒和钙中毒使催化剂的表面酸量降低。钾和钙中毒造成中温SCR催化剂的脱硝活性降低,并且Ca中毒造成的催化剂活性降低要明显高于K中毒。
  • 图  1  SCR实验装置示意图

    Figure  1  Schematic diagram of experimental apparatus for SCR

    1: reaction gases; 2: mass flow rate controller; 3: mixer; 4: preheater; 5: temperature controller; 6: heater; 7: catalytic reactor; 8: flue gas analyzer; 9: gas valve; 10: gas sampling point

    图  2  三种不同催化剂的吸附脱附等温线

    Figure  2  Adsorption desorption isotherms of three kinds of catalysts

    图  3  三种催化剂的BJH孔径分布曲线

    Figure  3  BJH pore size distribution curves of three kinds of catalysts

    图  4  不同催化剂的扫描电镜照片

    Figure  4  SEM images of different catalysts

    (a): F-SCR; (b): K-SCR; (c): Ca-SCR

    图  5  三种催化剂的V 2p XPS谱图

    Figure  5  V 2p XPS spectra of three kinds of catalysts

    图  6  三种催化剂的O 1s XPS谱图

    Figure  6  O 1s XPS spectra of three kinds of catalysts

    图  7  不同催化剂的NH3-TPD谱图

    Figure  7  NH3-TPD profiles of different catalysts

    a: F-SCR; b: K-SCR; c: Ca-SCR

    图  8  不同催化剂的H2-TPR谱图

    Figure  8  H2-TPR profiles of different catalysts

    a: K-SCR; b: Ca-SCR; c: F-SCR

    图  9  碱金属(K)中毒对SCR催化剂性能的影响

    Figure  9  Effect of K poisoning on the properties of SCR catalyst

    (reaction conditions: NO 0.06%,NH3 0.066%,O2 6%,GHSV: 30000h-1)□: K/V(mol ratio)=0; ○: K/V(mol ratio)=1; △: K/V(mol ratio)=2; ▽: K/V(mol ratio)=3

    图  10  碱土金属(Ca)中毒对SCR催化剂性能的影响

    Figure  10  Effect of Ca poisoning on the performance of SCR catalyst

    (reaction conditions: NO 0.06%,NH3 0.066%,O2 6%,GHSV: 30000h-1)□: Ca/V(mol ratio)=0; ○: Ca/V(mol ratio)=1; △: Ca/V(mol ratio)=2; ▽: Ca/V(mol ratio)=3

    表  1  不同催化剂的BET分析

    Table  1  BET analysis of different catalysts

    Catalyst typeBET surface area A/(m2·g-1)Pore volume v/(cm3·g-1)Pore diameter d/nm
    F-SCR94.680.313011.908
    K-SCR71.480.288814.665
    Ca-SCR87.960.291512.306
    下载: 导出CSV

    表  2  三种催化剂中V5+和V4+的含量

    Table  2  Percentage of V4+ and V5+ in three kinds of catalysts

    CatalystPercentage w/%
    V5+/(V5++V4+)V4+/(V5++V4+)
    F-SCR93.386.62
    K-SCR89.3710.63
    Ca-SCR7.4892.52
    下载: 导出CSV

    表  3  三种催化剂中晶格氧(Oa)和化学吸附氧(Ob)所占的百分含量

    Table  3  Oxygen analysis of three kinds of catalysts

    F-SCRK-SCRCa-SCR
    Oa /%58.8962.1259.64
    Ob /%41.1137.8840.36
    下载: 导出CSV

    表  4  催化剂中毒后效率下降百分数

    Table  4  Efficiency decrease caused by catalyst poisoning

    CatalystDecrease in efficiency /%
    250℃300℃350℃400℃
    K-SCR(K/V=1)44.610.812.85.5
    K-SCR(K/V=3)6032.425.613.3
    Ca-SCR(Ca/V=1)41.514.911.69.1
    Ca-SCR(Ca/V=3)64.648.636.063.0
    下载: 导出CSV
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出版历程
  • 收稿日期:  2015-10-16
  • 修回日期:  2015-12-02
  • 网络出版日期:  2021-01-23
  • 刊出日期:  2016-04-30

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