Analysis of the competitive reaction rates of dibenzothiophene and naphthalene in the hydrodenitrogenation of 1,2,3,4-tetrahydroquinoline over Pt-based catalysts

Xue Yifan; Zhao Fei; Feng Jie; Li Wenying

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Analysis of the competitive reaction rates of dibenzothiophene and naphthalene in the hydrodenitrogenation of 1,2,3,4-tetrahydroquinoline over Pt-based catalysts

Updated：2026-05-14

- Analysis of the competitive reaction rates of dibenzothiophene and naphthalene in the hydrodenitrogenation of 1,2,3,4-tetrahydroquinoline over Pt-based catalysts
- Chinese Journal of Chemical Engineering Vol. 90, Issue 2, Pages: 94-105(2026)
- Affiliations：
  
  State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China
  Beijing Huairou Laboratory, Beijing 101499, China
  Shanxi Research Institute of Huairou Laboratory, Taiyuan 030032, China
- Author bio：
  
  Corresponding author. E-mail address: fengjie@tyut.edu.cn (J. Feng).
- Funds：
- DOI：
  CLC：
- Received：28 May 2025，
  
  Revised：2025-09-28，
  
  Accepted：28 September 2025，
  
  Online First：09 December 2025，
  
  Published：2026-02
- Accepted：
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Xue Yifan, Zhao Fei, Feng Jie, et al. Analysis of the competitive reaction rates of dibenzothiophene and naphthalene in the hydrodenitrogenation of 1,2,3,4-tetrahydroquinoline over Pt-based catalysts[J]. Chinese Journal of Chemical Engineering, 2026, 90(2): 94-105.
DOI：

Xue Yifan, Zhao Fei, Feng Jie, et al. Analysis of the competitive reaction rates of dibenzothiophene and naphthalene in the hydrodenitrogenation of 1,2,3,4-tetrahydroquinoline over Pt-based catalysts[J]. Chinese Journal of Chemical Engineering, 2026, 90(2): 94-105. DOI：

摘要

Abstract

In hydrofining processes

the competitive interactions among sulfur-containing compounds

aromatic hydrocarbons

and nitrogen-containing intermediates fundamentally govern catalytic performance. Nevertheless

the complex kinetic relationships within hydrodenitrogenation (HDN) systems have remained unclear and insufficiently investigated. This research c

omprehensively and systematically examined the competitive reaction kinetics of naphthalene (an aromatic model) and dibenzothiophene (a sulfur-based model) during the HDN of 1

4-tetrahydroquinoline over Pt-based catalysts. Through systematic analysis of conversion rates and product distributions across various reaction conditions

it demonstrated that both dibenzothiophene and naphthalene exert distinct inhibitory effects on HDN through mechanistically differentiated pathways. Quantitative evaluation revealed a pronounced temperature dependence in mitigating these inhibitory effects

whereas pressure variations exhibited negligible influence. These findings collectively demonstrate that surface adsorption competition

rather than hydrogen availability

dictates the reaction kinetics. Rigorous kinetic calculations and rate constant fittings identified the hydrogenation of 1

4-tetrahydroquinoline to decahydroquinoline as the rate-limiting step susceptible to competitive inhibition. This phenomenon predominantly arises from the tripartite competitive adsorption among naphthalene

dibenzothiophene

and 1

4-tetrahydroquinoline at catalytic active sites

as corroborated by theoretical adsorption energy calculations. Notably

the two inhibitors manifest divergent interaction mechanisms: H

ions generated during H

S formation in dibenzothiophene desulfurization facilitate C—N bond cleavage

whereas naphthalene directly suppresses this critical step. Furthermore

atomic-layer-deposited TiO

on Pt/Al

engineered the catalyst surface through three synergistic effects: enhanced nitrogen adsorption capacity

optimized hydrogen spillover

and generation of additional C—N bond cleavage sites. This multi-effect strategy effectively reduces the negative impacts of competitive adsorption

emphasizing the crucial role of competitive reaction kinetics in designing sulfur/aromatic-resistant HDN catalysts.

关键词

Keywords

references

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