Mn掺杂对尖晶石型NiFe1.97Pd0.03O4-δ催化剂脱硝性能的影响

doi:10.16085/j.issn.1000-6613.2019-0276

摘要/Abstract

摘要：

采用生物模板法，通过掺杂Mn对尖晶石型NiFe_1.97Pd_0.03O_4-_δ催化剂中的Fe离子进行取代，制备一系列不同Mn掺杂量的NiFe_1.97-_xMn_xPd_0.03O_4-_δ催化剂（x=0、0.01、0.02、0.05、0.10），并在单管固定床反应器中进行H₂-SCR脱硝性能评价。运用X射线衍射仪（XRD）、场发射扫描电子显微镜（FE-SEM）、程序升温-脱附（NH₃-TPD）和程序升温还原（H₂-TPR）以及傅里叶红外光谱仪（FTIR）等手段对催化剂进行表征、分析。结果表明：适量Mn的掺杂不仅可以提高活性物种Pd在催化剂上的分散度，还显著提高了其催化剂表面的总酸量及其氧化还原能力，从而提高了NiFe_1.97Pd_0.03O_4-_δ催化剂在低温下的H₂-SCR脱硝活性，并拓宽了其催化活性温度窗口。在实验范围内，NiFe_1.92Mn_0.05Pd_0.03O_4-_δ催化剂在150℃下的NO转化率高达95%，且在150~200℃温度区间内，NO转化率均在90%以上。

关键词: 生物模板, 尖晶石, Mn掺杂, H₂-SCR, 催化剂

Abstract:

Spinel catalyst NiFe_1.97-_xMn_xPd_0.03O_4-_δ was prepared by using a biological template and then was applied for the selective catalytic reduction of NO with hydrogen(H₂-SCR) in a single-tube fix-bed reactor. A series of spinel catalysts was obtained by doping Mn with different molar ratio of Mn to Ni. The catalysts were characterized by X-ray diffraction（XRD）, field emission scanning electron microscope (FE-SEM), Fourier transform infrared spectroscopy（FTIR）, NH₃ temperature-programmed desorption (NH₃-TPD) and H₂ temperature-programmed reduction (H₂-TPR). The results indicated that the catalysts doped with suitable amount of Mn had significantly improved the dispersion of the active specie Pd, the total acid content on the catalyst surface and the ability to oxidation, leading to enhanced de-NO_xperformance of NiFe_1.97Pd_0.03O_4-_δcatalyst at low temperature and a broadened active temperature window. Within the scope of the experiments, the NO conversion of NiFe_1.92Mn_0.05Pd_0.03O_4-_δcatalyst was up to 95% at 150℃, and maintained above 90% at 150—200℃.

Key words: bio-templating, spinel, Mn-doping, H₂-SCR, catalyst

中图分类号:

O643.36

赵跃飞,闫涛涛,陈凯,霍超. Mn掺杂对尖晶石型NiFe_1.97Pd_0.03O_4-_δ催化剂脱硝性能的影响[J]. 化工进展, 2020, 39(2): 577-583.

Yuefei ZHAO,Taotao YAN,Kai CHEN,Chao HUO. Effect of Mn-doped spinel catalyst NiFe_1.97Pd_0.03O_4-_δon catalytic performance for SCR[J]. Chemical Industry and Engineering Progress, 2020, 39(2): 577-583.

图/表 8

表1 实验所用试剂与药品

名称	分子式	规格	厂家
九水硝酸铁	Fe(NO₃)₃·9H₂O	分析纯	上海阿拉丁生物科技有限公司
六水硝酸镍	Ni(NO₃)₃·6H₂O	分析纯	上海阿拉丁生物科技有限公司
氯化钯	PdCl₂	分析纯	上海麦克林生物科技有限公司
硝酸锰溶液（50%）	Mn(NO₃)₂	分析纯	上海华精生物高科技有限公式
氨水	NH₄OH	分析纯	杭州龙山精细化工有限公司
脱脂棉	(C₆H₁₀O₅)_n	优级	盐城市心宜敷料用品厂

图1 NiFe1.97-xMnxPd0.03O4-δ催化剂的H2-SCR催化性能

图2 NiFe1.97-xMnxPd0.03O4催化剂的XRD谱图与（311）晶面XRD峰位置

(1)—NiFe1.97Pd0.03O4-δ;(2)—NiFe1.96Mn0.01Pd0.03O4-δ;(3)—NiFe1.95Mn0.02Pd0.03O4-δ;(4)—NiFe1.92Mn0.05Pd0.03O4-δ;(5)—NiFe1.87Mn0.10Pd0.03O4-δ

图3 NiFe1.97-xMnxPd0.03O4-δ催化剂红外吸收光谱图

(1)—NiFe1.97Pd0.03O4-δ;(2)—NiFe1.96Mn0.01Pd0.03O4-δ;(3)—NiFe1.95Mn0.02Pd0.03O4-δ;(4)—NiFe1.92Mn0.05Pd0.03O4-δ;(5)—NiFe1.87Mn0.10Pd0.03O4-δ

图4 NiFe1.97-xMnxPd0.03O4催化剂FE-SEM图

图5 NiFe1.97-xMnxPd0.03O4催化剂的NH3-TPD谱图

(1)—NiFe1.97Pd0.03O4-δ;(2)—NiFe1.96Mn0.01Pd0.03O4-δ;(3)—NiFe1.95Mn0.02Pd0.03O4-δ;(4)—NiFe1.92Mn0.05Pd0.03O4-δ;(5)—NiFe1.87Mn0.10Pd0.03O4-δ

表2 NiFe1.97-xMnxPd0.03O4催化剂NH3脱附峰面积

x	$S N H 3 - T P D$
0.00	25.17
0.01	46.22
0.02	48.12
0.05	51.54
0.10	78.77

表2 NiFe1.97-xMnxPd0.03O4催化剂NH3脱附峰面积

x	$S N H 3 - T P D$
0.00	25.17
0.01	46.22
0.02	48.12
0.05	51.54
0.10	78.77

图6 NiFe1.97-xMnxPd0.03O4-δ催化剂的H2-TPR-MS谱图

(1)—NiFe1.97Pd0.03O4-δ;(2)—NiFe1.96Mn0.01Pd0.03O4-δ;(3)—NiFe1.95Mn0.02Pd0.03O4-δ;(4)—NiFe1.92Mn0.05Pd0.03O4-δ;(5)—NiFe1.87Mn0.10Pd0.03O4-δ

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