Effect of Shell Thickness on Skeletal Fe@HZSM-5 Core-Shell Catalysts for Fischer-Tropsch Synthesis

doi:10.6023/A20120563

Acta Chimica Sinica ›› 2021, Vol. 79 ›› Issue (6): 771-777.DOI: 10.6023/A20120563 Previous Articles Next Articles

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壳层厚度对骨架Fe@HZSM-5核壳催化剂费托合成催化性能的影响

孙冬^a, 孙博^a, 裴燕^a, 闫世润^a, 范康年^a, 乔明华^a^,^*(), 张晓昕^b, 宗保宁^b^,^*()

a 复旦大学化学系上海市分子催化和功能材料重点实验室上海 200438
b 中国石化石油化工科学研究院催化材料与反应工程国家重点实验室北京 100083

投稿日期:2020-12-27 发布日期:2021-05-31
通讯作者: 乔明华, 宗保宁
基金资助:
国家重点研发专项项目(2018YFB0604501); 国家自然科学基金(21872035); 上海师范大学资源化学国际联合实验室(IJLRC)开放课题; 上海市科委科技基金(19DZ2270100)

Effect of Shell Thickness on Skeletal Fe@HZSM-5 Core-Shell Catalysts for Fischer-Tropsch Synthesis

Dong Sun^a, Bo Sun^a, Yan Pei^a, Shirun Yan^a, Kangnian Fan^a, Minghua Qiao^a(), Xiaoxin Zhang^b, Baoning Zong^b()

a Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai 200438, China
b State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China

Received:2020-12-27 Published:2021-05-31
Contact: Minghua Qiao, Baoning Zong
Supported by:
National Key Research and Development Project of China(2018YFB0604501); National Natural Science Foundation of China(21872035); International Joint Laboratory on Resource Chemistry (IJLRC) of Shanghai Normal University; Science and Technology Commission of Shanghai Municipality(19DZ2270100)

Using the Raney Fe-Al alloy as the precursor for Fe and Al, and tetrapropylammonium hydroxide (TPAOH) as both the base for the leaching of the alloy and the template for the synthesis of HZSM-5, we synthesized the skeletal Fe core-HZSM-5 shell catalysts (Raney Fe@HZSM-5) via a facile one-pot hydrothermal strategy. The thickness of the zeolite shell was adjusted by varying the hydrothermal time. The catalysts were characterized by inductively coupled plasma-atomic emission spectroscopy (ICP-AES), N₂ physisorption, X-ray powder diffraction (XRD), temperature-programmed desorption of NH₃ (NH₃-TPD), and scanning electron microscopy (SEM). It was identified that the Raney Fe-Al alloy was more suitable than the rapidly quenched Fe-Al alloy as the precursor to the skeletal Fe core, since the skeletal Fe catalyst alkali-leached from the former produced more long-chain hydrocarbons during the Fischer-Tropsch synthesis (FTS) reaction for successive cracking and isomerization. A complete HZSM-5 shell was obtained only after above 24 h of hydrothermal treatment. With the hydrothermal time from 2 d to 8 d, the thickness of the compact HZSM-5 shell increased from 1.3 μm to 9.7 μm, the relative crystallinity increased steadily, while the SiO₂/Al₂O₃ ratio remained essentially constant, and the amount of the acid sites is parallel to the thickness of the zeolite shell. In the FTS reaction using syngas with the H₂/CO molar ratio of 2 and at 543 K and 2.0 MPa, the CO conversion and the selectivity to the gasoline fraction (C₅~C₁₁ hydrocarbons) evolved in a volcanic trend with the shell thickness, suggesting the existence of an optimal amount of the acid sites, while less or more is adverse to the activity and selectivity to the gasoline fraction. The Raney Fe@HZSM-5 catalyst hydrothermally treated for 4 d exhibited the highest CO conversion of 92% and the selectivity to the gasoline fraction of 71%, along with an iso-paraffin to n-paraffin ratio of 1.9. At the n(H₂)/n(CO) ratio of 1, the selectivity to the gasoline fraction and the iso-paraffin to n-paraffin ratio were further improved to 73% and 2.1, respectively, which shows promise for this catalyst to transform the coal- or biomass- derived syngas to high-octane number gasoline.

Key words: skeletal Fe, HZSM-5, core-shell structure, Fischer-Tropsch synthesis, gasoline

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Dong Sun, Bo Sun, Yan Pei, Shirun Yan, Kangnian Fan, Minghua Qiao, Xiaoxin Zhang, Baoning Zong. Effect of Shell Thickness on Skeletal Fe@HZSM-5 Core-Shell Catalysts for Fischer-Tropsch Synthesis[J]. Acta Chimica Sinica, 2021, 79(6): 771-777.

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Fig. & Tab. 8

Figure 1. (a) CO conversions and (b, c) hydrocarbon distributions over the Raney Fe and RQ Fe catalysts in the FTS reaction

Figure 2. SEM images of the Fe@Z-5 catalysts after (a) 2 h, (b) 12 h, and (c) 24 h of hydrothermal treatment

Figure 3. XRD patterns of the Fe@Z-5 catalysts with different hydrothermal time ? HZSM-5, □ γ-Fe2O3

Figure 4. SEM images of the (a) Raney Fe and (b) Fe@Z-5-4d catalysts

Figure 5. Cross-sectional SEM images of the Fe@Z-5 catalysts with different hydrothermal time. (a) Fe@Z-5-2d, (b) Fe@Z-5-4d, (c) Fe@Z-5-6d, and (d) Fe@Z-5-8d

Catalyst	S_BET^a/(m²•g^-1)	V_pore/(cm³•g^-1)	d_pore/nm	w(Zeolite)/%	SiO₂/Al₂O₃^b (molar ratio)	Relative crystallinity/%	NH₃ uptake ^c/(µmol•g^-1)
Fe@Z-5-2d	100	0.12	6.54	7.9	62	73	38.5
Fe@Z-5-4d	116	0.08	6.47	12.5	63	76	56.1
Fe@Z-5-6d	121	0.10	6.39	20.8	63	89	77.6
Fe@Z-5-8d	132	0.14	6.08	25.1	63	100	94.5

Table 1. The physicochemical properties of the Fe@Z-5 catalysts with different hydrothermal time

Catalyst	X_CO/%	S_CO2/%	S_hydrocarbon^b/%				C_i/C_n^c	O/P^d
Catalyst	X_CO/%	S_CO2/%	CH₄	C₂~C₄	C₅~C₁₁	C₁₂₊	C_i/C_n^c	O/P^d
Fe@Z-5-2d	71	18	11	23	61	5.3	0.7	0.4
Fe@Z-5-4d	92	13	7.7	21	71	—	1.9	0.5
Fe@Z-5-6d	87	16	12	24	64	—	2.1	0.3
Fe@Z-5-8d	77	13	16	30	55	—	2.4	0.3

Table 2. Catalytic performances of the Fe@Z-5 catalysts with different hydrothermal time in the FTS reactiona

Figure 6. The FTS results over the Fe@Z-5-4d catalyst after 150 h on stream using syngas with different H2/CO molar ratios

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壳层厚度对骨架Fe@HZSM-5核壳催化剂费托合成催化性能的影响

Effect of Shell Thickness on Skeletal Fe@HZSM-5 Core-Shell Catalysts for Fischer-Tropsch Synthesis

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