Mn/Ce改性菱铁矿催化剂在SCR脱硝反应中的特性研究

WEI Yu-liang; GUI Ke-ting; LIU Xiang-xiang; LIANG Hui; GU Shao-chen; REN Dong-dong

Mn/Ce改性菱铁矿催化剂在SCR脱硝反应中的特性研究

东南大学能源与环境学院, 能源热转换及其过程测控教育部重点实验室, 江苏南京 210096

基金项目:

the National Natural Science Foundation of China 51276039

Environmental Protection Research Project of Jiangsu Province 2015008

详细信息

中图分类号: X511
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- 被引次数: 0
出版历程
- 收稿日期: 2019-09-03
- 修回日期: 2019-11-12
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-12-10

Performance of Mn-Ce co-doped siderite catalysts in the selective catalytic reduction of NO_x by NH₃

Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096, China

Funds:

the National Natural Science Foundation of China 51276039

Environmental Protection Research Project of Jiangsu Province 2015008

More Information

Corresponding author: GUI Ke-ting, E-mail: ktgui@seu.edu.cn

摘要

摘要: 富含过渡元素的菱铁矿是用于制备选择性催化还原（SCR）脱硝催化剂的理想材料。在本研究中，对菱铁矿掺杂了Mn和Ce，并研究了Mn-Ce共掺杂改性菱铁矿在NH₃-SCR反应中去除NO_x的活性。结果表明，经过450℃煅烧后菱铁矿的主要成分FeCO₃能够转化为Fe₂O₃。菱铁矿掺杂Mn和Ce后能够提高比表面积和表面酸度，降低硫酸铵盐在催化剂表面上的热稳定性。因此，Mn-Ce共掺杂改性菱铁矿催化剂表现出较高的SCR脱硝活性和抗硫性。3% Mn1% Ce-菱铁矿催化剂在脱硝效率高于90%的温度窗口能够拓宽至180-300℃，同时在引入SO₂ 7.5 h后该催化剂的脱硝效率仍高于75%。
- Mn-Ce共掺杂 /
- 菱铁矿 /
- 选择性催化还原 /
- 脱硝 /
- 抗硫性
Abstract: Siderite, rich in the transition elements, is an idea material to prepare the catalysts for the selective catalytic reduction (SCR) of NO_x by NH₃. In this work, siderite was doped with Mn and Ce and the performance of Mn-Ce co-doped siderite catalysts in the removal of NO_x (de-NO_x) by SCR with NH₃ was then investigated. The results illustrate that FeCO₃ as the main component of siderite can be converted into Fe₂O₃ by calcination at 450℃. The doping of siderite with Mn and Ce can enhance the surface area and acidity of siderite and reduce the thermal stability of ammonium sulfate formed on the catalyst surface. As a result, the Mn-Ce co-doped siderite catalysts exhibit high efficiency in the de-NO_x by SCR and high resistance against sulfur. Over the 3%Mn1%Ce-siderite catalyst, high NO_x conversion (>90%) is achieved in the temperature window of 180-300℃; moreover, the NO_x conversion remains above 75% even after introducing SO₂ for 7.5 h.
- Mn-Ce co-doping /
- siderite /
- selective catalytic reduction /
- de-NO_x /
- sulfur resistance

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Figure 1 Flow chart for the preparation of Mn and Ce co-doped siderite catalyst

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Figure 2 Schematic diagram of the device for the catalytic tests in the SCR of NO_x by NH₃

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Figure 3 Conversion of NO_x for the de-NO_x reaction by SCR with NH₃ over the siderite catalysts calcined at different temperatures

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Figure 4 Conversion of NO_x for the de-NO_x reaction by SCR with NH₃ over the Mn-modified siderite catalysts with different Mn doping amounts

■: siderite; ●: 1%Mn-siderite; ▲: 2%Mn-siderite; ▼: 3%Mn-siderite

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Figure 5 XRD patterns of the unmodified siderite (a) and 3%Mn-siderite (b) catalysts

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Figure 6 Conversion of NO_x for the de-NO_x reaction by SCR with NH₃ over the Mn and Ce modified siderite catalysts (a): siderite doped with Ce; (b): siderite co-doped with Mn and Ce

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Figure 7 XRD patterns of various siderite catalysts co-doped with Mn and Ce

a: 1%Mn1%Ce-siderite; b: 2%Mn1%Ce-siderite; c: 3%Mn1%Ce-siderite; d: 3%Mn1.5%Ce-siderite; e: 3%Mn0.5%Ce-siderite

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Figure 8 NH₃-TPD profiles of various siderite catalysts co-doped with Mn and Ce

a: 3%Mn1%Ce-siderite; b: 3%Mn1.5%Ce-siderite; c: 2%Mn1%Ce-siderite; d: 3%Mn0.5%Ce-siderite; e: 1%Mn1%Ce-siderite

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Figure 9 Sulfur resistance of the unmodified siderite (a) and 3%Mn1%Ce-siderite (b) catalysts in the SCR de-NO_x reactions

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Figure 10 TGA profiles of the spent siderite (a) and 3%Mn1%Ce-siderite (b) catalysts after the sulfur resistance tests for the SCR de-NO_x reaction

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Table 1 Textural properties of the siderite catalysts calcined at different temperatures

Calc. temperature t/℃	Surface area A/(m²·g^-1)	Pore volume v /(cm³·g^-1)	Pore size d/nm
Uncalcined	21.5	0.025	4.7
400	42.8	0.055	4.8
450	64.8	0.138	9.7
500	58.4	0.133	9.1

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Table 2 XRF analysis results of various Mn-modified siderite catalysts

Sample	Composition w/%
Sample	Fe	Mn	Si	Al	Mg
Siderite	44.25	2.941	1.053	0.2834	0.4112
1%Mn-siderite	43.69	3.953	0.9820	0.2152	0.7329
2%Mn-siderite	42.94	5.074	0.9240	0.1978	0.6765
3%Mn-siderite	42.19	5.981	0.9060	0.1939	0.4534

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Table 3 Textural properties of various Mn-modified siderite catalysts

Sample	Surface area A/(m²·g^-1)	Pore volume v /(cm³·g^-1)	Pore size d /nm
Siderite	64.8	0.138	9.7
1%Mn-siderite	68.4	0.133	8.7
2%Mn-siderite	71.0	0.146	8.2
3%Mn-siderite	73.2	0.137	7.5

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Table 4 Experimental group setting for the investigation of the effect of Mn and Ce co-doping on the performance of modified siderite catalyst

Test number	Mn doping amount /%	Ce doping amount /%
1	0	0
2	3.0	0.5
3	3.0	1.0
4	3.0	1.5
5	1.0	1.0
6	2.0	1.0

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