The Promotion Effect of Introducing H2S into the Feed Gas on the Propane Dehydrogenation Reaction

doi:10.12422/j.issn.1672-6952.2026.05.003

Abstract

Abstract:

Density functional theory (DFT) calculations and catalyst performance evaluations were conducted to investigate the promoting effect of H2S on the dehydrogenation performance of the PtSnK/Al2O3 catalyst. The results show that adding an appropriate amount of H2S to the feed gas significantly increases propylene selectivity, which remains above 93%, while improving catalyst stability and reducing carbon deposition. The optimal H2S volume fraction in the feed is 2.4×10⁻5, at which both propane conversion and propylene selectivity reach their maximum values. Excessive H2S, however, causes catalyst poisoning and a substantial decrease in activity. According to the DFT calculation results, among different adsorption configurations, the Gibbs free energy is minimal when H2S and propylene are co⁃adsorbed on both Pt(111) and Pt(211) crystal surfaces. Specifically, the Gibbs free energy on the Pt(211) crystal surface is -0.09 eV, which is lower than that on the Pt(111) crystal surface, which is -0.05 eV. These results suggest that H2S facilitates propylene desorption and preferentially adsorbs on the Pt(211) surface, thereby suppressing side reactions, increasing propylene selectivity, and promoting the dehydrogenation performance of the PtSnK/Al2O3 catalyst.

Key words: Pt?based catalyst, Propane dehydrogenation, Propylene selectivity, DFT calculations

摘要：

通过密度泛函理论（DFT）计算及催化剂性能评价，探究了H2S对PtSnK/Al2O3催化剂脱氢性能的促进作用。结果表明，原料气中加入适量的H2S后，丙烯选择性明显增加，且始终保持在93%以上，催化剂稳定性提升，积碳量明显降低；原料中H2S的最佳体积分数为2.4×10-5，此时丙烷转化率与丙烯选择性均达到最大值，但H2S过量时会导致催化剂中毒，活性大幅度下降。根据DFT计算结果，在不同吸附构型中，H2S与丙烯共同吸附在Pt(111)晶面与Pt(211)晶面时的Gibbs自由能均最小，其中Pt(211)晶面的Gibbs自由能为-0.09 eV，小于Pt(111)晶面的-0.05 eV。这表明H2S的存在有利于丙烯脱附，且通过H2S优先吸附在Pt(211)晶面抑制副反应，从而提高丙烯选择性，对PtSnK/Al2O3催化剂的催化性能具有明显的促进作用。

关键词: Pt基催化剂, 丙烷脱氢, 丙烯选择性, DFT计算

CLC Number:

TE624.9

Qihang LU, Shuqi WANG, Haotian CHI, Haijuan ZHANG. The Promotion Effect of Introducing H₂S into the Feed Gas on the Propane Dehydrogenation Reaction[J]. Journal of Liaoning Petrochemical University, 2026, 46(5): 16-21.

路启航, 王淑琪, 迟昊天, 张海娟. 原料气中引入H₂S对丙烷脱氢反应的促进作用[J]. 辽宁石油化工大学学报, 2026, 46(5): 16-21.

Figures/Tables 7

Fig.1 Effect of H2S volume fraction on propane dehydrogenation performance

Table 1 Analysis of carbon deposition on the catalyst

H₂S体积分数×10⁵	w（C）/%	w（H）/%	n（H）/n（C）
0	3.51	1.14	3.90
1.0	3.65	2.92	9.59
2.4	2.51	3.86	18.48
5.0	0.94	1.88	24.00

Fig.2 Raman spectra of the catalyst

Fig.3 Adsorption configuration of propylene separately adsorbed on the Pt(111) and Pt(211) crystal planes

Fig.4 Adsorption configurations of H2S and propylene co?adsorbed on Pt(111) and Pt(211) crystal planes

Table 2 Adsorption energies and favorable positions of sulfur species on Pt(111) and Pt(211) crystal planes

晶面	有利位置	ΔE/eV
Pt(111)	顶部	-0.83
Pt(211)	顶部	-0.97

Fig.5 Gibbs free energy of different adsorption configurations on Pt(111) and Pt(211) crystal planes

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The Promotion Effect of Introducing H₂S into the Feed Gas on the Propane Dehydrogenation Reaction

原料气中引入H₂S对丙烷脱氢反应的促进作用

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