Fe助剂对PtFe/Silicalite-1催化剂丙烷脱氢性能影响研究

doi:10.6023/A25070260

摘要/Abstract

贵金属Pt凭借其卓越的C—H键活化能力及较低的C—C键断裂倾向被广泛用于丙烷脱氢反应. 但传统Pt基催化剂在丙烷脱氢反应过程中积碳快速沉积会覆盖活性位点导致催化剂失活, 且频繁再生会引发活性位结构不可逆改变, 造成永久性失活. 因此高活性、高稳定性Pt基催化剂的开发是关键. 本研究采用共浸渍法, 以三氯化铁为Fe前驱体, 将Pt与不同负载量(质量分数0.1%~2.0%)的Fe共同负载于Silicalite-1分子筛, 制备了PtFe/Silicalite-1 (PtFe/S-1)系列催化剂, 并对其丙烷脱氢性能展开研究. 结果显示, Fe的引入能有效增强Pt与载体相互作用, 使Pt物种分散度提高, 从而形成具有高稳定性的小尺寸Pt物种. 同时Fe通过电子转移调控Pt的电子结构, 从而提高丙烯选择性. Fe负载量对催化性能影响显著, 低负载时催化剂活性低、稳定性差, 高负载则因副反应导致初始丙烯选择性下降, 而Pt1.0Fe/S-1催化剂综合性能最优, 初始丙烷转化率为59.8%, 6 h后仍保持52.9%, 丙烯选择性从89.1%提升至96.4%, 表明适量Fe(质量分数1.0%)可通过提高Pt分散度、调控Pt电子性质, 实现催化活性与稳定性的平衡, 为高效丙烷脱氢催化剂的设计提供了重要参考.

关键词: 丙烷脱氢, 丙烯, Pt基催化剂, Fe助剂效应

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

引用此文

王嘉玮, 张宁, 范晓强, 孔莲, 赵震. Fe助剂对PtFe/Silicalite-1催化剂丙烷脱氢性能影响研究[J]. 化学学报, 2025, 83(12): 1498-1506.

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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图/表 12

图1. 焙烧(A)和还原后(B) PtFe/S-1催化剂的XRD图

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

图2. 焙烧后PtFe/S-1催化剂的(A) N2-吸附脱附等温线及(B)孔径分布图

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

表1. PtFe/S-1催化剂的织构性能参数

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

图3. (A)焙烧后PtFe/S-1催化剂与(B)相应Fe/S-1样品的H2-TPR曲线图

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

图4. 还原后PtFe/S-1催化剂的Raman谱图

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

图5. 还原后PtFe/S-1催化剂的SEM照片

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

图6. 还原后PtFe/S-1的Fe 2p (A)与Pt 4f (B) XPS谱图

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

图7. 还原后PtFe/S-1催化剂的TEM照片

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

图8. PtFe/S-1催化剂的CO-DRIFT谱图

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

图9. 1.0Fe/S-1和PtFe/S-1催化剂上(A)丙烷转化率和(B)丙烯选择性随时间变化关系图; (C) PtFe/S-1催化剂的活化能

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

表2. PtFe/S-1和1.0Fe/S-1催化剂的丙烷脱氢性能

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

图10. 丙烷脱氢反应6 h后PtFe/S-1催化剂的TG图

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

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