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锰氧化物的低浓度甲烷催化氧化性能研究
Study on catalytic oxidation performance of manganese oxides for low concentration methane
- 低碳化学与化工 2025, 50(9): 10-16.
- 作者机构：
1.中煤昔阳能源有限责任公司白羊岭煤矿，山西 晋中 045300
2.清华大学 山西清洁能源研究院，山西 太原 030032
3.太原理工大学 化学与化工学院，山西 太原 030024
4.怀柔实验室山西研究院，山西 太原 030032
- 作者简介：
吕人杰（1981—），本科，高级工程师，研究方向为煤矿瓦斯、水和火等重大灾害治理与新技术，E-mail：63682264@qq.com。
樊昱辰（1997—），硕士，助理工程师，研究方向为煤矿瓦斯治理，E-mail：fycsxhd@163.com。
- 基金信息：
DOI：10.12434/j.issn.2097-2547.20240491
中图分类号： TQ426;X505收稿日期：2024-12-11，
修回日期：2025-02-10，
纸质出版日期：2025-09-25
- 稿件说明：
移动端阅览
吕人杰,樊昱辰,刘祎琳等.锰氧化物的低浓度甲烷催化氧化性能研究[J].低碳化学与化工,2025,50(09):10-16.
LV Renjie,FAN Yuchen,LIU Yilin,et al.Study on catalytic oxidation performance of manganese oxides for low concentration methane[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(09):10-16.
吕人杰,樊昱辰,刘祎琳等.锰氧化物的低浓度甲烷催化氧化性能研究[J].低碳化学与化工,2025,50(09):10-16. DOI： 10.12434/j.issn.2097-2547.20240491.
LV Renjie,FAN Yuchen,LIU Yilin,et al.Study on catalytic oxidation performance of manganese oxides for low concentration methane[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(09):10-16. DOI： 10.12434/j.issn.2097-2547.20240491.
摘要
煤矿开采过程中的风排瓦斯是重要的甲烷排放源，由于甲烷浓度低、排量大等特点造成其规模化处理难度较大。催化氧化技术能够在较低温度下有效去除低浓度甲烷，该技术的关键在于研发低成本、高性能的催化剂。选用不同价态和晶型的锰氧化物作为催化剂，在固定床中探究了其对低浓度甲烷的催化氧化性能，利用TG、XRD、SEM、XPS和H
2
-TPR等手段对催化剂的理化性质进行了表征分析并探讨了可能的反应机理。结果表明，MnO
2
（
β
-MnO
2
）相较于Mn
2
O
3
具有更高的催化活性，MnO
2
的起活温度（
t
10
）和完全氧化温度（
t
90
）分别为365 ℃和505 ℃，显著低于Mn
2
O
3
（
t
10
= 655 ℃，
t
90
= 795 ℃）。TG分析表明MnO
2
在550 ℃以上会逐渐失氧转变为Mn
2
O
3
，这可能会导致催化剂的活性发生变化。在同一价态下，
α-
MnO
2
较
β
-MnO
2
具有更高的甲烷催化氧化性能，
α-
MnO
2
的
t
90
为433 ℃。H
2
-TPR分
析表明
α-
MnO
2
具有较低的还原温度，晶格氧活性更强。
α-
MnO
2
在550 ℃下经过24 h的反应后甲烷转化率下降了近8%，这表明未来仍需进一步提升锰氧化物的稳定性。本研究可为经济高效锰基催化剂的开发提供参考。
Abstract
The ventilation air methane emitted during coal mining is a significant source of methane emissions. Due to the low concentration and large emission of methane
its large-scale treatment is difficult. Catalytic oxidation technology can effectively remove low-concentration methane at relatively low temperatures
with a key focus on developing low-cost and high-performance catalysts. Manganese oxides with different oxidation valance states and crystal phases were investigated to explore the catalytic oxidation performances of low concentration methane in a fixed-bed reactor. TG
XRD
SEM
XPS and H
2
-TPR were used to characterize and analyze the physicochemical properties of catalysts and explore the possible reaction mechanisms. The results show that MnO
2
(
β
-MnO
2
) has higher catalytic activity than Mn
2
O
3
and the activation temperature (
t
10
) and complete oxidation temperature (
t
90
) of MnO
2
are 365 ℃ and 505 ℃
respectively
which are significantly lower than those of Mn
2
O
3
(
t
10
= 655 ℃
t
90
= 795 ℃). TG analysis shows that MnO
2
gradually losts oxygen and transforms into Mn
2
O
3
above 550 ℃
which may affect the activity of catalysts. At the same valence state
α
-MnO
2
demonstrates superior methane catalytic oxidation performance compared to
β
-MnO
2
.
t
90
of
α
-MnO
2
is 433 ℃. The H
2
-TPR results shows that
α
-MnO
2
has a lower reducing temperature and thus higher lattice oxygen activity. After 24 h r
eaction at 550 ℃
the methane conversion rate of
α
-MnO
2
decreases by approximately 8%
indicating that further improvements are needed to enhance the stability of manganese oxides catalysts. This study can provide reference for the development of cost-effective manganese-based catalysts for methane oxidation.
关键词
Keywords
references
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