载体对负载型NiSn催化剂丙烷脱氢性能的影响

张焕玲; 王国玮; 山红红; 李春义

载体对负载型NiSn催化剂丙烷脱氢性能的影响

中国石油大学(华东) 重质油国家重点实验室, 山东青岛 266580

基金项目:

国家自然科学基金 21606257

国家自然科学基金 U1362201

详细信息

中图分类号: TQ536.9
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- 被引次数: 0
出版历程
- 收稿日期: 2017-07-07
- 修回日期: 2017-09-30
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-12-10

Propane dehydrogenation over NiSn-based catalysts

State Key Laboratory of Heavy Oil Processing, China University of Petroleum(East China), Qingdao 266580, China

Funds:

the National Natural Science Foundation of China 21606257

the National Natural Science Foundation of China U1362201

More Information

Corresponding author: WANG Guo-wei, Tel:86981260, E-mail:wangguowei@upc.edu.cn

摘要

摘要: 研究了载体对负载型NiSn催化剂丙烷脱氢性能的影响，主要对比考察了以SiO₂、MgO、Al₂O₃、MgAl₂O₄为载体的NiSn催化剂的丙烷脱氢性能。采用X射线衍射技术（XRD）、氮气吸附-脱附技术、氨气程序升温脱附技术（NH₃-TPD）以及氢气程序升温还原技术（H₂-TPR）对催化剂样品进行表征。结果表明，SiO₂因具有较大的比表面积、大孔径、酸性较弱等特点，以其为载体制备所得催化剂中Ni_2.67Sn₂组分含量高，催化剂性能较高。
- 丙烷脱氢 /
- NiSn催化剂 /
- 载体
Abstract: In this paper, we studied the effects of supports, such as SiO₂, MgO, Al₂O₃ and MgAl₂O₄, on the performance of supported NiSn catalyst for propane dehydrogenation. NH₃ temperature-programmed desorption, H₂ temperature-programmed reduction were applied for the characterization of the catalysts. The results show that SiO₂ with large specific surface area and large pore size can achieve good contact between catalyst and reactants, leading to a high content of Ni_2.67Sn₂ alloy and a reduced diffusion resistance, In addition, their weak acid improve dehydrogenation activity and propene selectivity.
- propane dehydrogenation /
- NiSn-based catalysts /
- support

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图 1 不同载体的NiSn催化剂的XRD谱图

Figure 1 XRD patterns of NiSn catalysts with different supports

★: Ni_2.67Sn₂; ◆: carriers; ↑: SnO; ↓: Ni₃Sn₂

下载: 全尺寸图片幻灯片

图 2 不同载体NiSn催化剂的氮气吸附-脱附等温线和孔径分布

Figure 2 Nitrogen adsorption-desorption isotherms and pore-size distributions of NiSn catalyst with different supports

■: 5NiSn/SiO₂; ●: 5NiSn/Al₂O₃; ▲: 5NiSn/MgAl₂O₄; ▼: 5NiSn/MgO

下载: 全尺寸图片幻灯片

图 3 不同载体的NiSn催化剂的H₂-TPR谱图

Figure 3 H₂-TPR profiles of NiSn catalyst with different supports

下载: 全尺寸图片幻灯片

图 4 不同载体的NiSn催化剂的NH₃-TPD谱图

Figure 4 NH₃-TPD profiles of NiSn catalysts with different carriers

下载: 全尺寸图片幻灯片

图 5 不同载体对丙烷脱氢转化率的影响

Figure 5 Conversion of propane on the NiSn catalysts with different supports

reaction conditions: t=600 ℃, p=1.01×10⁵ Pa, F_propane=5 mL/min

下载: 全尺寸图片幻灯片

图 6 不同载体的NiSn催化剂丙烷转化率和比表面积的关系

Figure 6 Relationship between conversion and specific surface area of NiSn catalysts with different supports

下载: 全尺寸图片幻灯片

图 7 不同载体对丙烯选择性的影响

Figure 7 Selectivity to propene on NiSn catalysts with different supports

reaction conditions: t=600 ℃, p=1.01×10⁵ Pa, F_propane=5 mL/min

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表 1 不同载体NiSn催化剂的结构性质

Table 1 Textural properties of NiSn catalysts with different supports

Sample	A_BET/(m²·g^-1)	v_pore/(mL·g^-1)	d_pore/nm	d_c/nm
5NiSn/SiO₂	253	0.98	11.4	48.8
5NiSn/Al₂O₃	138	0.21	3.6	46.2
5NiSn/MgAl₂O₄	91	0.21	6.2	38.0
5NiSn/MgO	25	0.19	25.2	44.4
A_BET: BET specific area; v_pore: pore volume; d_pore: average pore diameter; d_c: crystallite size determined by scherrer’s equation

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表 2 不同载体NiSn催化剂的酸量分布

Table 2 The amount of acid on NiSn catalysts with different supports

Catalyst	t_M/℃			Total acid content/(mmol·g^-1 _cat)^*	Peak fraction/%
Catalyst	Ⅰ	Ⅱ	Ⅲ	Total acid content/(mmol·g^-1 _cat)^*	Ⅰ	Ⅱ	Ⅲ
5NiSn/SiO₂	187	245	358	0.30	34.1	52.7	13.2
5NiSn/Al₂O₃	175	231	328	0.50	21.7	31.8	46.5
5NiSn/MgAl₂O₄	184	243	334	0.31	22.8	50.9	26.3
5NiSn/MgO	176	262	365	0.08	45.2	32.8	22.0
^*: the amount of acid is calculated as the amount of ammonia adsorbed per gram of catalyst t_M: the temperature of the highest desorption peak

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