不同拓扑结构分子筛催化剂上正十二烷异构化反应性能比较研究

刘佳; 宋兆阳; 李思洁; 周明东; 李蕾; 凌凤香

doi:10.19906/j.cnki.JFCT.2023067

不同拓扑结构分子筛催化剂上正十二烷异构化反应性能比较研究

doi: 10.19906/j.cnki.JFCT.2023067

刘佳^1,,
宋兆阳^2,,
李思洁^2,,
周明东^1,,
李蕾^1,,
凌凤香^2, ,

1.
辽宁石油化工大学石油化工学院, 辽宁抚顺113001
2.
中石化(大连)石油化工研究院有限公司, 辽宁大连116045)

基金项目: 中国石油化工股份有限公司资助项目（420014）资助

详细信息

通讯作者:
Tel: 041139699307， E-mail: lingfengxiang.fshy@sinopec.com

中图分类号: TQ426.95
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出版历程
- 收稿日期: 2023-08-17
- 修回日期: 2023-09-13
- 录用日期: 2023-09-13
- 网络出版日期: 2023-09-18
- 刊出日期: 2023-10-10

Comparative study on the performance of n-dodecane isomerization reaction on molecular sieve catalysts with different topological structures

1.
LiaoNing Petrochemical University, Fushun 113001, China
2.
SINOPEC (Dalian) Research Institute of Petroleum and Petrochemicals Co., Ltd, Dalian 116045, China

Funds: The project was supported by China Petrochemical Corporation Limited (420014).

摘要

摘要: 采用硅铝比相近的Y分子筛、ZSM-5分子筛和β分子筛分别负载贵金属约0.5% Pt 制备催化剂，通过XRD、XRF、TEM、N₂物理吸附-脱附、NH₃-TPD、Py-FTIR、²⁷Al核磁等手段研究了不同拓扑结构分子筛晶体结构、元素组成、孔结构、酸性以及Al分布的差异，进而考察了拓扑结构对催化剂催化正十二烷异构化反应性能的影响。结果表明，当硅铝比接近时，ZSM-5分子筛总酸量及骨架铝比例最高、平均孔径最小，Y分子筛总酸量及骨架铝比例最低、平均孔径最大，而β分子筛的总酸量、骨架铝比例以及平均孔径介于两者之间，说明不同拓扑结构分子筛硅铝原子组合方式不同，不仅影响孔道结构和孔口尺寸，而且会因为铝所处位置的不同而影响酸性；在正十二烷异构化反应中，Pt/ZSM-5催化剂活性最高且主要发生的是外表面无选择性反应，Pt/Y催化剂活性最低且异构化反应主要在孔道内，而Pt/β催化剂活性介于两者之间，异构化反应发生于孔口处以锁匙反应为主。
- 硅铝比相近 /
- β分子筛 /
- Y分子筛 /
- ZSM-5分子筛 /
- 拓扑结构 /
- 异构化
Abstract: The catalysts were prepared by loading about 0.5% Pt noble metal on Y molecular sieves, ZSM-5 molecular sieves and β molecular sieves with similar Si/Al ratios. The crystal structures of the molecular sieves with different topologies, elemental compositions, pore structures, activities, and Al distributions were investigated by means of XRD, XRF, TEM, N₂ physical adsorption and desorption, NH₃-TPD, Py-FTIR, and ²⁷Al NMR. And then the effect of topology on the catalytic performance of n-dodecane isomerization reaction was investigated. The results showed that when the Si/Al ratios were close to each other, the ZSM-5 molecular sieve had the highest total acid and skeleton Al ratio and the smallest average pore size, the Y molecular sieve had the lowest total acid and skeleton Al ratio and the largest average pore size, and the β molecular sieve's total acid, skeleton Al ratio, and average pore size were between the two others, which indicated that different topologies of the molecular sieves with different combinations of Si/Al atoms affected not only the structure of the pores and the size of the pore but also the number of acidity. In the n-dodecane isomerization reaction, the Pt/ZSM-5 catalyst had the highest activity and the main reaction occurred on the outer surface without selectivity, the Pt/Y catalyst had the lowest activity and the isomerization reaction mainly occurred inside the pores, while the Pt/β catalyst had the activity between the other two catalysts and the isomerization reaction occurred dominantly at the pore opening as the key-locking reaction.
- similar Si/Al ratio /
- β-molecular sieve /
- Y-molecular sieve /
- ZSM-5 molecular sieve /
- topological /
- isomerization

HTML全文

FIG. 2703. FIG. 2703.

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图 1 (a) β分子筛、(b) Y分子筛和(c) ZSM-5分子筛的拓扑结构图示意^[25-28]

Figure 1 Topology diagram of (a) β molecular sieve, (b) Y molecular sieve, and (c) ZSM-5 molecular sieve^[25-28]

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图 2 分子筛与催化剂的XRD谱图

Figure 2 XRD patterns of molecular sieves and catalysts

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图 3 （a) Pt/β、(b) Pt/Y、(c) Pt/ZSM-5的TEM照片

Figure 3 TEM images of (a) Pt/β, (b) Pt/Y, and (c) Pt/ZSM-5

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图 4 Pt/β、Pt/Y、Pt/ZSM-5的N₂吸附-脱附等温曲线

Figure 4 N₂ isothermal adsorption-desorption curves of (a) Pt/β, (b) Pt/Y, (c) Pt/ZSM-5

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图 5 Pt/β、Pt/Y、Pt/ZSM-5的NH₃-TPD谱图

Figure 5 NH₃-TPD spectra of Pt/β, Pt/Y, Pt/ZSM-5

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图 6 Pt/β、Pt/Y、Pt/ZSM-5的Py-FTIR谱图

Figure 6 Py-FTIR spectra of Pt/β, Pt/Y, Pt/ZSM-5

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图 7 Pt/β、Pt/Y和Pt/ZSM-5的27Al-NMR谱图

Figure 7 27Al-NMR spectra of (a) Pt/β, (b) Pt/Y and (c) Pt/ZSM-5

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图 8 Pt/β、Pt/Y、Pt/ZSM-5正十二烷异构化反应性能

Figure 8 Results of Pt/β (a), Pt/Y (b), Pt/ZSM-5 (c) n-dodecane isomerization reactions

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图 9 (a) 2-甲基十一烷，(b) 3-甲基十一烷，(c) 4-甲基十一烷和(d)5和6甲基十一烷选择性

Figure 9 Selectivity of (a) 2-methylundecane, (b) 3-methylundecane, (c) 4-methylundecane, and (d) 5 + 6-methylundecane

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图 10 Pt/β、Pt/Y、Pt/ZSM-5多甲基异构体选择性

Figure 10 Selectivity of Pt/β, Pt/Y, Pt/ZSM-5 multibranch isomers

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图 11 Pt/β、Pt/Y、Pt/ZSM-5稳定性

Figure 11 Stability of Pt/β, Pt/Y, and Pt/ZSM-5

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图 12 不同结构分子筛上异构化反应路径示意图

Figure 12 A schematic diagram of the isomerization pathways on different molecular sieves

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表 1 Pt/β、Pt/Y、Pt/ZSM-5三种催化剂的主要组成

Table 1 Main components of Pt/β, Pt/Y and Pt/ZSM-5 catalysts

Catalyst	SiO₂ /%	Al₂O₃ /%	n_SiO₂/n_Al₂O₃	Pt /%
Pt/β	94.90	4.60	35.1	0.50
Pt/Y	94.80	4.71	34.2	0.49
Pt/ZSM-5	95.05	4.46	36.2	0.49

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表 2 Pt/β、Pt/Y、Pt/ZSM-5的孔结构参数

Table 2 Pore structure parameters of Pt/β, Pt/Y, Pt/ZSM-5

Sample	S_BET / (m²·g⁻¹)	S_micro / (m²·g⁻¹)	S_meso / (m²·g⁻¹)	v_micro / (cm³·g⁻¹)	v_meso / (cm³·g⁻¹)	Average pore diameter / nm
Pt/β	613	567	46	0.43	0.20	4.11
Pt/Y	627	565	61	0.43	0.22	4.15
Pt/ZSM-5	332	322	10	0.18	0.03	2.53

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表 3 Pt/β、Pt/Y、Pt/ZSM-5的酸分布

Table 3 Acid distribution parameter of Pt/β, Pt/Y, Pt/ZSM-5

Sample	Weak / (cm³·g⁻¹)	Weak /%	Medium / (cm³·g⁻¹)	Medium /%	Strong / (cm³·g⁻¹)	Strong /%	Total
Pt/β	4.53	33.9	8.48	63.4	0.36	2.7	13.37
Pt/Y	0.41	33.3	0.73	59.7	0.09	7.0	1.23
Pt/ZSM-5	9.19	44.4	6.39	30.9	5.11	24.7	20.69

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