Preparation of Fe@Si/S-34 Catalysts and Its Catalytic Performance for Syngas to Olefins

doi:10.6023/A22070329

Abstract

The direct synthesis of light olefins from syngas via Fischer-Tropsch synthesis reaction is a promising technology for direct synthesis of olefins from syngas. The key is to improve the selectivity of light olefins through the regulation of product distribution. In this work, the hydrophobic Fe@Si catalyst was prepared by room temperature solid state method- Stöber-silylation method, and then the catalyst was combined with SAPO-34 molecular sieves with different contents to prepare Fe@Si/S-34 composite catalysts. The effects of SAPO-34 molecular sieve content on the physicochemical properties of the catalysts were investigated by X-ray diffraction, scanning electron microscopy, N₂ adsorption-desorption, NH₃ temperature programmed desorption and water contact angle measurement. The results showed that the content of SAPO-34 molecular sieve has significant influence on the surface area, pore volume, acidity and hydrophobicity of the catalysts. With the increase of SAPO-34 molecular sieve content, the specific surface area and total pore volume of the catalyst increased, the weak acid and medium-strong acid sites increased, and the hydrophobicity weakened. The catalytic performance evaluation results showed that the Fe@Si/S-34 composite catalyst decomposed C₅₊ hydrocarbons into light hydrocarbons, significantly reduced the selectivity of C₅₊ products and increased the selectivity of C₂~C₄ hydrocarbons. Appropriate SAPO-34 molecular sieve could significantly improve the selectivity of C₂~C₄ olefins. When the mass ratio of Fe@Si catalyst to SAPO-34 is 2, the C₂~C₄ olefin selectivity of Fe@Si/S-34 catalyst is the highest, the conversion of CO is 80.0%, the selectivity of CO₂ in the product is 8.9%, and the selectivity of C₂~C₄ olefins is 31.1%. In this study, the hydrophobicity of Fe@Si catalyst and the cracking activity of SAPO-34 molecular sieve for C₅₊ hydrocarbon were coupled together to inhibit the water-gas shift (WGS) reaction, reduce the CO₂ selectivity and obtain higher C₂~C₄ olefin selectivity, which provided a new strategy for the development of catalysts for Fischer-Tropsch synthesis to olefins.

Key words: syngas, light olefins, Fischer-Tropsch synthesis, hydrophobic catalyst, SAPO-34 molecular sieve

Cite this article

Zhiping Chen, Yongle Meng, Jing Lu, Wenwu Zhou, Zhiyuan Yang, Anning Zhou. Preparation of Fe@Si/S-34 Catalysts and Its Catalytic Performance for Syngas to Olefins[J]. Acta Chimica Sinica, 2023, 81(1): 14-19.

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Fig. & Tab. 10

Figure 1. XRD patterns of Fe@Si and Fe@Si/S-34 catalysts

Figure 2. SEM images of (a) Fe@Si, (b) Fe@Si/S-34-1, (c) Fe@Si/S-34-2 and (d) Fe@Si/S-34-3

Figure 3. N2 adsorption-desorption isothermal curves of Fe@Si and Fe@Si/S-34 catalysts

Sample	S_BET/ (m²•g^-1)	S_mic/ (m²•g^-1)	S_ext/ (m²•g^-1)	V_t/ (cm³•g^-1)	V_mic/ (cm³•g^-1)	V_mes/ (cm³•g^-1)
Fe@Si	4.06	1.75	2.31	0.019	0.001	0.018
Fe@Si/S-34-1	174.11	170.23	3.87	0.118	0.084	0.033
Fe@Si/S-34-2	228.42	214.92	13.49	0.144	0.106	0.038
Fe@Si/S-34-3	308.81	302.64	6.17	0.176	0.149	0.027

Table 1. The texture properties of Fe@Si and Fe@Si/S-34 catalysts

Figure 4. NH3-TPD spectra of Fe@Si and Fe@Si/S-34 catalysts

Figure 5. Water-droplet contact angles of (a) Fe@Si, (b) Fe@Si/S-34-1, (c) Fe@Si/S-34-2 and (d) Fe@Si/S-34-3

Figure 6. FTO performance of Fe@Si/S-34-2 catalyst at different reaction temperatures

Figure 7. Stability evaluation of Fe@Si/S-34-2 catalyst

Figure 8. Catalytic performances of the Fe@Si/S-34 catalysts with different SAPO-34 content in FTO reaction

催化剂	CO转化率/%	CO₂ 选择性/%	烃分布/%				C₂⁼~C₄⁼ 收率/%
催化剂	CO转化率/%	CO₂ 选择性/%	CH₄	C₂⁼~C₄⁼	C₂⁰~C₄⁰	C₅₊	C₂⁼~C₄⁼ 收率/%
FeMnK/S-34^a^[20]	86.3	28.1	14.9	23.8	5.8	55.5	14.8
FeMnNa^b^[22]	64.3	54.8	40.1	35.0	13.4	11.5	10.2
FeMnNa/S-34^b^[22]	64.1	45.1	33.1	40.3	11.2	15.4	14.2
FeZnNa/S-34^c^[31]	92.6	54.6	15.9	38.6	9.2	36.3	17.8
FeKS/S-34^d^[32]	45.8	48.7	14.0	39.1	7.7	36.3	17.9
Fe@Si/S-34-2^e	80.0	7.2	20.7	34.2	27.6	17.5	24.9

Table 2. Comparison of the catalytic performance of Fe@Si/S-34-2 with the works reported in the literatures

References 35

[1]	Zhao, S.; Li, H.; Wang, B.; Yang, X.; Peng, Y.; Du, H.; Zhang, Y.; Han, D.; Li, Z. Fuel 2022, 321, 124124. doi: 10.1016/j.fuel.2022.124124
[2]	Qi, Z.; Gao, F.; Zhou, C.; Zeng, Y.; Wu, Q.; Yang, L.; Wang, X.; Hu, Z. Acta Chim. Sinica 2022, 80, 1100. (in Chinese) doi: 10.6023/A22030139
	( 齐志豪, 高福杰, 周常楷, 曾誉, 吴强, 杨立军, 王喜章, 胡征, 化学学报, 2022, 80, 1100.) doi: 10.6023/A22030139
[3]	Liu, Z.; Ni, Y.; Hu, Z.; Fu, Y.; Fang, X.; Jiang, Q.; Chen, Z.; Zhu, W.; Liu, Z. Chinese J. Catal. 2022, 43, 877. doi: 10.1016/S1872-2067(21)63908-6
[4]	Chen, Z.; Zhang, Z.; Zhou, W.; Yang, Z.; Zhou, A. J. Fuel Chem. Technol. 2022, 50, 1381. (in Chinese)
	( 陈治平, 张智, 周文武, 杨志远, 周安宁, 燃料化学学报, 2022, 50, 1381.)
[5]	Sun, D.; Sun, B.; Pei, Y.; Yan, S.; Fan, K.; Qiao, M.; Zhang, X.; Zong, B. Acta Chim. Sinica 2021, 79, 771. (in Chinese) doi: 10.6023/A20120563
	( 孙冬, 孙博, 裴燕, 闫世润, 范康年, 乔明华, 张晓昕, 宗保宁, 化学学报, 2021, 79, 771.) doi: 10.6023/A20120563
[6]	Cheng, K.; Kang, J.; King, D.; Subramanian, V.; Zhou, C.; Zhang, Q.; Wang, Y. Adv. Catal. 2017, 60, 125.
[7]	Li, Y.; Zhang, X.; Wei, M. Chinese J. Catal. 2018, 39, 1329. doi: 10.1016/S1872-2067(18)63100-6
[8]	Hondo, E.; Lu, P.; Zhang, P.; Li, J.; Tsubaki, N. J. Jpn. Petrol. Inst. 2020, 63, 239. doi: 10.1627/jpi.63.239
[9]	Zhai, P.; Li, Y.; Wang, M.; Liu, J.; Cao, Z.; Zhang, J.; Xu, Y.; Liu, X.; Li, Y.; Zhu, Q.; Xiao, D.; Wen, X.; Ma, D. Chem 2021, 7, 3027. doi: 10.1016/j.chempr.2021.08.019
[10]	Wang, D.; Chen, B.; Duan, X.; Chen, D.; Zhou, X. J. Energy Chem. 2016, 25, 911. doi: 10.1016/j.jechem.2016.11.002
[11]	Masudi, A.; Jusoh, N.; Muraza, O. Catal. Sci. Technol. 2020, 10, 1582. doi: 10.1039/C9CY01875A
[12]	Jiao, F.; Li, J.; Pan, X.; Xiao, J.; Li, H.; Ma, H.; Wei, M.; Pan, Y.; Zhou, Z.; Li, M.; Miao, S.; Li, J.; Zhu, Y.; Xiao, D.; He, T.; Yang, J.; Qi, F.; Fu, Q.; Bao, X. Science 2016, 351, 1065. doi: 10.1126/science.aaf1835
[13]	Liu, Z. Acta Phys. Chim. Sin. 2016, 32, 803. (in Chinese) doi: 10.3866/PKU.WHXB2016032801
	( 刘忠范, 物理化学学报, 2016, 32, 803.)
[14]	Liu, J.; Song, Y.; Guo, X.; Song, C.; Guo, X. Chinese J. Catal. 2022, 43, 731. doi: 10.1016/S1872-2067(21)63802-0
[15]	Yang, X.; Guo, X.; Zhang, C.; Wang, X.; Yang, Y.; Li, Y. Acta Chim. Sinica 2017, 75, 360. (in Chinese) doi: 10.6023/A16100549
	( 杨向平, 郭晓雪, 张成华, 王小萍, 杨勇, 李永旺, 化学学报, 2017, 75, 360.) doi: 10.6023/A16100549
[16]	Fellenz, N.; Bengoa, J.; Cagnoli, M.; Marchetti, S. J. Porous Mat. 2017, 24, 1025. doi: 10.1007/s10934-016-0342-5
[17]	Yu, X.; Zhang, J.; Wang, X.; Ma, Q.; Gao, X.; Xia, H.; Lai, X.; Fan, S.; Zhao, T. Appl. Catal. B-Environ. 2018, 232, 420. doi: 10.1016/j.apcatb.2018.03.048
[18]	Xu, Y.; Li, X.; Gao, J.; Wang, J.; Ma, G.; Wen, X.; Yang, Y.; Li, Y.; Ding, M. Science 2021, 371, 610. doi: 10.1126/science.abb3649
[19]	Karre, A.; Dadyburjor, D. Chem. Eng. Commun. 2022, 209, 967. doi: 10.1080/00986445.2021.1935252
[20]	Cai, Z. M.S. Thesis, Zhejiang university, Hangzhou, 2017. (in Chinese)
	( 蔡正才, 硕士论文, 浙江大学, 杭州, 2017.)
[21]	Qiu, T.; Wang, L.; Lv, S.; Sun, B.; Zhang, Y.; Liu, Z.; Yang, W.; Li, J. Fuel 2017, 203, 811. doi: 10.1016/j.fuel.2017.05.043
[22]	Di, Z.; Zhao, T.; Feng, X.; Luo, M. Catal. Lett. 2019, 149, 441. doi: 10.1007/s10562-018-2624-9
[23]	Cheng, K.; Gu, B.; Liu, X.; Kang, J.; Zhang, Q.; Wang, Y. Angew. Chem. Int. Ed. 2016, 55, 4725. doi: 10.1002/anie.201601208 pmid: 26961855
[24]	Liu, X.; Zhou, W.; Yang, Y.; Cheng, K.; Kang, J.; Zhang, L.; Zhang, G.; Min, X.; Zhang, Q.; Wang, Y. Chem. Sci. 2018, 9, 4708. doi: 10.1039/C8SC01597J
[25]	Zhang, S.; Wen, Z.; Yang, L.; Duan, C.; Lu, X.; Song, Y.; Ge, Q.; Fang, Y. Micropor. Mesopor. Mater. 2019, 274, 220. doi: 10.1016/j.micromeso.2018.08.001
[26]	Yang, M.; Tian, P.; Wang, C.; Yuan, Y.; Yang, Y.; Xu, S.; He, Y.; Liu, Z. ChemComm 2014, 50, 1845.
[27]	Tong, M.; Chizema, L.; Chang, X.; Hondo, E.; Dai, L.; Zeng, Y.; Zeng, C.; Ahmad, H.; Yang, R.; Lu, P. Micropor. Mesopor. Mater. 2021, 320, 111105. doi: 10.1016/j.micromeso.2021.111105
[28]	Shi, L.; Li, D.; Hou, B.; Sun, Y. Chinese J. Catal. 2007, 28, 999. doi: 10.1016/S1872-2067(07)60084-9
[29]	Vatanpour, V.; Esmaeili, M.; Chahvari, S.; Masteri, M. J. Environ. Chem. Eng. 2021, 9, 105900. doi: 10.1016/j.jece.2021.105900
[30]	Junaidi, M.; Leo, C.; Ahmad, A.; Ahmad, N. Micropor. Mesopor. Mater. 2015, 206, 23. doi: 10.1016/j.micromeso.2014.12.013
[31]	Hou, Y. M.S. Thesis, Shaanxi Normal University, Xi'an, 2020. (in Chinese)
	( 候屹峰, 硕士论文, 陕西师范大学, 西安, 2020.)
[32]	Wang, H. Ph.D. Dissertation, Tianjin university, Tianjin, 2019. (in Chinese)
	( 王洪宇, 博士论文, 天津大学, 天津, 2019.)
[33]	Tong, A.; Dan, D.; Yi, C. Chem. Res. Chin. Univ. 2017, 33, 672. doi: 10.1007/s40242-017-6316-6
[34]	Li, J.; Pan, X.; Bao, X. Chinese J. Catal. 2015, 36, 1131. doi: 10.1016/S1872-2067(14)60297-7
[35]	Tan, L.; Wang, F.; Zhang, P.; Suzuki, Y.; Wu, Y.; Chen, J.; Yang, G.; Tsubaki, N. Chem. Sci. 2020, 11, 4097. doi: 10.1039/c9sc05544d pmid: 34122875

Fe@Si/S-34催化剂的制备及其合成气制烯烃性能