Study on the Influence of Fe Promoter on Propane Dehydrogenation Performance of PtFe/Silicalite-1 Catalyst

doi:10.6023/A25070260

Abstract

Noble metal Pt is widely applied in propane dehydrogenation reaction due to its excellent ability to activate C—H bonds and its relatively low tendency to break C—C bonds. However, in the course of propane dehydrogenation catalyzed by traditional Pt-based catalysts, the rapid deposition of coke can cover the active sites, which in turn leads to the deactivation of the catalyst. Furthermore, frequent regeneration will trigger irreversible changes in the structure of the active sites, resulting in permanent deactivation. Therefore, the development of Pt-based catalysts with high activity and high stability is of crucial significance. In this work, PtFe/Silicalite-1 (PtFe/S-1) catalysts with different Fe loadings (mass fraction from 0.1% to 2.0%) were prepared by co-impregnation method, and their performance in propane dehydrogenation was investigated. The results indicate that the introduction of Fe can effectively strengthen the interaction between Pt and the support, enhance the dispersion of Pt species, and thus form small-sized Pt species with high stability. At the same time, Fe regulates the electronic structure of Pt through electron transfer, thereby improving the selectivity towards propylene. The loading amount of Fe has a significant impact on the catalytic performance: when the loading is low, the catalyst exhibits low activity and poor stability; when the loading is high, the initial propylene selectivity decreases due to side reactions. Among them, the Pt1.0Fe/S-1 catalyst shows the highest propane dehydrogenation performance, with the initial propane conversion of 59.8%, which still remains at 52.9% after 6 h, and the propylene selectivity increases from 89.1% to 96.4%. This finding demonstrates that an appropriate amount of Fe (mass fraction 1.0%) can achieve a balance between catalytic activity and stability by improving Pt dispersion, regulating the electronic properties of Pt, thus providing an important reference for the design of efficient propane dehydrogenation catalysts.

Key words: propane dehydrogenation, propylene, Pt-based catalysts, Fe promoter effect

Cite this article

Jiawei Wang, Ning Zhang, Xiaoqiang Fan, Lian Kong, Zhen Zhao. Study on the Influence of Fe Promoter on Propane Dehydrogenation Performance of PtFe/Silicalite-1 Catalyst[J]. Acta Chimica Sinica, 2025, 83(12): 1498-1506.

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Fig. & Tab. 12

Figure 1. XRD patterns of calcined (A) and reduced (B) PtFe/S-1 catalysts

Figure 2. (A) N2 adsorption-desorption isotherms and (B) pore size distribution of the calcined PtFe/S-1 catalysts

Sample	S_mic^a/(m²•g⁻¹)	S_BET^b/(m²•g⁻¹)	d_ave^c/nm	d_BJH^d/nm	V_mic^e/(cm³•g⁻¹)	V_t^f/(cm³•g⁻¹)
Pt0.1Fe/S-1	221.5	434.5	2.4	4.4	0.11	0.26
Pt0.5Fe/S-1	208.4	423.5	2.4	4.5	0.11	0.25
Pt0.7Fe/S-1	206.0	407.3	2.4	4.5	0.11	0.24
Pt1.0Fe/S-1	251.5	376.3	2.3	4.4	0.13	0.22
Pt1.5Fe/S-1	260.3	392.5	2.3	4.5	0.13	0.23
Pt2.0Fe/S-1	248.4	366.9	2.3	4.6	0.13	0.21

Table 1. Textural properties of PtFe/S-1 catalysts

Figure 3. H2-TPR curves of (A) calcined PtFe/S-1 catalysts and (B) the corresponding Fe/S-1 samples

Figure 4. Raman spectra of the reduced PtFe/S-1 catalysts

Figure 5. SEM images of the reduced PtFe/S-1 catalysts

Figure 6. XPS spectra of Fe 2p (A) and Pt 4f (B) for the reduced PtFe/S-1 catalysts

Figure 7. TEM images of the reduced PtFe/S-1 catalyst

Figure 8. CO-DRIFT spectra of PtFe/S-1 catalysts

Figure 9. The relationship between (A) propane conversion and (B) propylene selectivity over time during propane dehydrogenation over 1.0Fe/S-1 and PtFe/S-1 catalysts; (C) Activation energy of PtFe/S-1 catalysts

Sample	Propane conversion/%			Propylene selectivity/%		k_d/h⁻¹
Sample	Initial	Final		Initial	Final	k_d/h⁻¹
Pt0.1Fe/S-1 Pt0.5Fe/S-1 Pt0.7Fe/S-1 Pt1.0Fe/S-1 Pt1.5Fe/S-1 Pt2.0Fe/S-1 1.0Fe/S-1	20.9 48.5 55.7 59.8 59.0 59.9 3.5	2.9 12.6 35.1 52.9 55.3 56.2 3.0		92.6 93.6 93.7 89.1 89.4 85.6 73.2	59.2 94.3 96.9 96.4 95.1 94.7 73.0	0.363 0.313 0.141 0.046 0.025 0.025 0.027

Table 2. Propane dehydrogenation performance of PtFe/S-1 and 1.0Fe/S-1 catalysts

Figure 10. TG curves of PtFe/S-1 catalysts after 6 h reaction

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Fe助剂对PtFe/Silicalite-1催化剂丙烷脱氢性能影响研究