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Al、Ti或Zr改性对包埋式Ni@SiO2催化剂甲烷部分氧化制合成气性能的影响
Effects of Al, Ti or Zr modification on performances of embedded Ni@SiO2 catalysts for partial oxidation of methane to syngas
- 低碳化学与化工 2024, 49(8): 66-73.
- 作者机构：
1.盐城工学院 化学化工学院,江苏 盐城 224051
2.南京工业大学 材料化学工程国家重点实验室,江苏 南京 211816
- 作者简介：
邵景玲（1982—），博士，讲师，研究方向为化学工艺，E-mail：jlshao@ycit.cn。
李 雷（1983—），博士，副教授，研究方向为环境与能源催化，E-mail：lee_ycit@hotmail.com。
- 基金信息：材料化学工程国家重点实验室自主课题(SKL-MCE-22B06)
DOI：10.12434/j.issn.2097-2547.20240008
中图分类号： TQ426;O643.36纸质出版日期：2024-08-25，
收稿日期：2024-01-05，
修回日期：2024-01-30，
- 稿件说明：
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邵景玲,李杰,费兆阳等.Al、Ti或Zr改性对包埋式Ni@SiO2催化剂甲烷部分氧化制合成气性能的影响[J].低碳化学与化工,2024,49(08):66-73.
SHAO Jingling,LI Jie,FEI Zhaoyang,et al.Effects of Al, Ti or Zr modification on performances of embedded Ni@SiO2 catalysts for partial oxidation of methane to syngas[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):66-73.
邵景玲,李杰,费兆阳等.Al、Ti或Zr改性对包埋式Ni@SiO2催化剂甲烷部分氧化制合成气性能的影响[J].低碳化学与化工,2024,49(08):66-73. DOI： 10.12434/j.issn.2097-2547.20240008.
SHAO Jingling,LI Jie,FEI Zhaoyang,et al.Effects of Al, Ti or Zr modification on performances of embedded Ni@SiO2 catalysts for partial oxidation of methane to syngas[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):66-73. DOI： 10.12434/j.issn.2097-2547.20240008.
摘要
包埋式结构催化剂能够有效地阻止活性组分的高温烧结，实现甲烷部分氧化（POM）反应高效制合成气。采用Stöber法制备了包埋式Ni@SiO
2
催化剂，并引入Al、Ti或Zr对其进行改性制得相应的改性催化剂。采用X射线衍射（XRD）、透射电镜（TEM）和N
2
吸/脱附等对催化剂的晶相结构、形貌和织构性质等进行了表征，并研究了改性对催化剂在POM反应制合成气（原料气组成：
V
(CH
4
):
V
(O
2
):
V
(N
2
)为2:1:3、流量为60 mL/min、压力为0.1 MPa、空速为7.2 L/(g·h)和反应时间为22 h）中催化性能的影响。结果表明，与Ni@SiO
2
相比，Ni@Al-SiO
2
可促进甲烷的活化，其催化性能明显提升，Ni@Ti-SiO
2
和Ni@Zr-SiO
2
因活性位点的阻碍而催化性能降低。在700 ℃下，反应稳定后，Ni@SiO
2
和Ni@Al-SiO
2
的CH
4
转化率分别为86%和80%，CO选择性均为90%左右，H
2
选择性分别为93%和88%。经8 h稳定性测试后，与Ni@SiO
2
相比，Ni@Ti-SiO
2
和Ni@Zr-SiO
2
的CH
4
转化率、CO选择性和H
2
选择性均明显降低。活性位点的减少和积炭是导致催化剂失活的主要原因，积炭未造成活性位点的完全覆盖，催化剂仍能保持稳定的POM催化性能。
Abstract
The embedded catalysts can effectively prevent the sintering behavior
and realize the high activity in partial oxidation of methane (POM) reaction. The embedded Ni@SiO
2
catalysts were prepared by Stöber method
and the Al
Ti or Zr were used to modify them. Various characterizations
such as X-ray diffraction (XRD)
transmission electron microscope (TEM) and N
2
adsorption/desorption
were employed to the characterizations of crystalline phase structures
morphologies and texture parameters of catalysts. The effects of modification of catalysts on the catalytic POM performance were further investigated under the feed gases compositions of
V
(CH
4
):
V
(O
2
):
V
(N
2
) of 2:1:3
gas flow rate of 60 mL/min
pressure of 0.1 MPa
space velocity of 7.2 L/(g·h) and reaction time of 22 h. The results show that compared with Ni@SiO
2
catalyst
the Ni@Al-SiO
2
catalyst can promote the activation of methane and its catalytic performance is improved. However
the Ni@Ti-SiO
2
and Ni@Zr-SiO
2
catalysts show the decreased catalytic performances because of the obstruction of active sites. At 700 ℃
the CH
4
conversation rates of Ni@Al-SiO
2
and Ni@SiO
2
are
86% and 80%
the CO selectivities are both about 90%
and the H
2
selectivities are 93% and 88%
respectively. However
compared with Ni@SiO
2
catalyst
the CH
4
conversion rates
CO selectivities and H
2
selectivities of Ni@Ti-SiO
2
and Ni@Zr-SiO
2
are significantly reduced. It reveals that the catalyst deactivation can be mainly ascribed to the loss of active sites and carbon deposit. But the active sites are not completely covered by deposited carbon
an
d the catalyst still maintain robust catalytic POM performance.
关键词
Ni@SiO2催化剂包埋式结构催化剂改性甲烷部分氧化积炭
Keywords
Ni@SiO2 catalystsembedded structurecatalyst modificationpartial oxidation of methanecarbon deposit
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