基于原位合成的Ni/Mg@MCM-41上的CO<sub>2</sub>甲烷化研究

王小柳; 杨萌; 朱玲君; 朱啸南; 王树荣

基于原位合成的Ni/Mg@MCM-41上的CO₂甲烷化研究

浙江大学能源清洁利用国家重点实验室, 浙江杭州 310027

基金项目:

国家杰出青年科学基金 51725603

详细信息

中图分类号: TK6
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- 被引次数: 0
出版历程
- 收稿日期: 2020-01-17
- 修回日期: 2020-03-08
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-04-10

CO₂ methanation over Ni/Mg@MCM-41 prepared by in-situ synthesis method

State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China

Funds:

the National Science Fund for Distinguished Young Scholars 51725603

More Information

Corresponding author: WANG Shu-rong, Tel: 0571-87952801, E-mail: srwang@zju.edu.cn

摘要

摘要: 通过原位引入Mg一步法合成了Mg@MCM-41复合介孔材料，并将其作为载体制备了高性能Ni基CO₂甲烷化催化剂。通过BET、XRD、TEM、CO₂-TPD、TG等手段对催化剂进行了表征分析，着重比较了Mg/Si物质的量比对于催化剂特性的影响。结果表明，当Mg/Si物质的量比为0.05时能够在不破坏孔道结构的前提下显著增加催化剂上的碱性位，有效地提高了催化剂对CO₂的吸附和活化，从而促进CO₂甲烷化反应过程中反应物的转化。实验所制得的催化剂均具有较好的热稳定性和催化反应活性，其中，Ni/0.05Mg@MCM-41在CO₂甲烷化反应表现出最优的催化性能，在320 ℃，1 MPa的条件下，CO₂转化率和CH₄选择性分别高达84.3%和97.8%。
- 二氧化碳 /
- 甲烷化 /
- 原位合成 /
- Mg@MCM-41 /
- 反应活性
Abstract: A series of xMg@MCM-41(x=0, 0.05, 0.1) functional mesoporous materials were synthesized by a novel in-situ one pot method and then were used as support for Ni based catalysts. The results of XRD and TEM show that when the amount of Mg/Si (molar ratio) is 0.05, Mg@MCM-4 with a regular and ordered mesoporous structure is synthesized where Mg is introduced into the framework of MCM-41. Introducing Mg into the framework of the support can significantly enhance the basic properties of the catalyst, thus promoting the adsorption and activation of CO₂. The catalysts prepared in the experiments all have good thermal stability and catalytic activity. Among them, Ni/0.05Mg@MCM-41 shows the best low temperature reaction activity in the CO₂ methanation reaction.
- CO₂ /
- methanation /
- in-situ /
- Mg@MCM-41 /
- catalytic activity

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图 1 八通道活性测试装置示意图

Figure 1 Scheme of the 8-channel parallel fixed-bed reactor (MPRS-8TS) at Zhejiang University

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图 2 N₂物理吸附-脱附等温曲线(a)和孔径分布(b)

Figure 2 N₂ adsorption-desorption isotherms (a) and pore size distribution curves of the catalysts (b)

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图 3 载体((a), (b))和还原后((c), (d))催化剂的XRD谱图

Figure 3 XRD patterns of the ((a), (b)) supports and ((c), (d)) reduced Ni based catalysts

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图 4 催化剂的H₂-TPR谱图

Figure 4 H₂-TPR profiles of the catalysts

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图 5 催化剂的CO₂-TPD谱图

Figure 5 CO₂-TPD profiles of the catalysts

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图 6 催化剂的TEM照片((a1), (a2))Ni/MCM-41，((b1), (b2))Ni/0.05Mg@MCM-41和((c1), (c2)) Ni/0.1Mg@MCM-41

Figure 6 TEM images of the catalysts((a1), (a2))Ni/MCM-41, ((b1), (b2)) Ni/0.05Mg@MCM-41 and ((c1), (c2))Ni/0.1Mg@MCM-41

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图 7 焙烧后催化剂的TG曲线

Figure 7 TG curves of the calcined catalysts

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图 8 催化剂CO₂甲烷化反应活性CO₂转化率(a), CH₄选择性(b), 320 ℃温度下催化剂的寿命评价(c)

Figure 8 Catalytic activity of the catalysts conversion of CO₂ (a), selectivity of CH₄ (b) and life test of the catalysts at 320 ℃ (c)

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表 1 催化剂的物理化学特性

Table 1 Physicochemical properties of the catalysts

Catalyst	A_BET /(m²·g^-1)	d_pore/ nm	v_pore/ (cm³·g^-1)	Mg/Si (molar ratio)	Theoretical/%		Actual w/%		d_Ni^a/nm
Catalyst	A_BET /(m²·g^-1)	d_pore/ nm	v_pore/ (cm³·g^-1)	Mg/Si (molar ratio)	Mg	Ni	Mg	Ni	d_Ni^a/nm
Ni/MCM-41	622.5	2.31	0.95	0	0	8.7	0.00	8.18	20
Ni/0.05Mg@MCM-41	606.3	3.37	0.84	0.05	1.78	8.7	1.94	8.28	15
Ni/0.1Mg@MCM-41	498.5	3.12	0.81	0.1	3.48	8.7	3.41	8.45	15
a: Ni size calculated by XRD

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