Mechanism of promoting COS-conversion via Ni additives in Zn-based desulfurizers for high-temperature desulfurization of coal gas

CHEN Sisi; DUAN Xinwei; HAN Bingying; MI Jie; WANG Jiancheng; WU Mengmeng

doi:10.11949/0438-1157.20260107

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Mechanism of promoting COS-conversion via Ni additives in Zn-based desulfurizers for high-temperature desulfurization of coal gas

更新时间：2026-06-12

- Mechanism of promoting COS-conversion via Ni additives in Zn-based desulfurizers for high-temperature desulfurization of coal gas
- CIESC Journal (2026)
- 作者机构：
  
  1.太原理工大学省部共建煤基能源清洁高效利用国家重点实验室，山西太原 030024
  2.太原理工大学煤科学与技术教育部重点实验室，山西太原 030024
  3.太原理工大学环境与生态学院，山西晋中 030600
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20260107
  CLC： TQ 546.5
- Received：22 January 2026，
  
  Revised：2026-06-11，
  
  Accepted：12 June 2026，
- 稿件说明：
移动端阅览
CHEN Sisi, DUAN Xinwei, HAN Bingying, et al. Mechanism of promoting COS-conversion via Ni additives in Zn-based desulfurizers for high-temperature desulfurization of coal gas[J/OL]. CIESC Journal, 2026.
DOI：

CHEN Sisi, DUAN Xinwei, HAN Bingying, et al. Mechanism of promoting COS-conversion via Ni additives in Zn-based desulfurizers for high-temperature desulfurization of coal gas[J/OL]. CIESC Journal, 2026. DOI： 10.11949/0438-1157.20260107.

摘要

高温煤气脱H

S是煤炭清洁高效利用的关键技术之一，但存在脱硫过程中COS生成的问题，而向高温脱硫剂中引入Ni助剂可有效抑制COS释放。课题组前期发现，Ni改性锌基脱硫剂吸硫饱和后可在无H

S气氛下显著促进COS氢解，但含H

S气氛下Ni助剂对COS氢解及水解的影响规律尚不清晰，阻碍了对助剂抑制放硫机制的深入认识。为此，本研究着重考察不同气氛（含H

S）和温度（400~600 °C）下Ni助剂对COS氢解/水解行为的促进/抑制作用，并结合密度泛函理论计算结果，揭示Ni助剂强化COS转化作用机制。结果表明，在COS+H

+CO+H

S气氛下，随着H

S浓度增加（100~2200 cm

·m

-3

），Ni助剂对COS氢解的催化活性逐渐减弱，但当H

S浓度≤1050 cm

·m

-3

（400~500 °C）时，Ni助剂仍能明显促进COS氢解（转化率较无助剂时增加34~75个百分点），表现出一定耐硫性；然而，在COS+H

O+CO+CO

S气氛下，Ni助剂对COS水解反应表现出较强抑制作用（COS基本不转化），且该抑制作用受温度影响较弱。ZnS(110)表面掺Ni后，增强了COS在固相表面的吸附（吸附能降低33 kJ·mol

-1

）和活化（与H

共存时，COS与Ni位点键合）；同时基于S与Ni原子的分波态密度分析发现，COS中S的3p轨道与Ni的3d轨道发生更强相互作用，上述特性改变表明固相表面对COS的吸附活化增强，这是Ni助剂强化COS氢解的主要原因。

Abstract

High-temperature coal gas desulfurization (H

S removal) is a key technology for the clean and efficient utilization of coal. However

a problem arises during this process: the formation of COS. Introducing the Ni additives into high-temperature desulfurizers can effectively suppress the release of COS. Our research group previously found that the Ni-modified zinc-based desulfurizers

after becoming saturated with sulfur

significantly promote COS hydrogenolysis in the absence of H

S. Nevertheless

the influence of the Ni additives on COS hydrogenolysis and hydrolysis in the presence

of H

S remains unclear

which hinders a deep understanding of the mechanism by which the additives suppress sulfur release. Therefore

this study focuses on investigating the promotional/inhibitory effects of the Ni additives on COS hydrogenolysis/hydrolysis under different atmospheres (containing H

S) and at different temperatures (400-600 °C). Combined with density functional theory calculation results

this work reveals the mechanism by which the Ni additives enhance COS conversion. The results show that

in the COS+H

+CO+H

S atmosphere

the catalytic activity of the Ni additives for COS hydrogenolysis gradually decreases with increasing H

S concentration (100-2200 cm

·m

-3

). However

when the H

S concentration is ≤1050 cm

·m

-3

(400-500 °C)

the Ni additives still significantly promote COS hydrogenolysis (the conversion rate increases by 34-75 percentage points compared to the system without the additives)

exhibiting a certain degree of sulfur tolerance. However

in the COS+H

O+CO+CO

S atmosphere

the Ni additives exhibit a strong inhibiting effect on COS hydrolysis (COS hardly converts)

and this inhibition is only weakly affected by the reaction temperature. After Ni doping on the ZnS(110) surface

the adsorption of COS on the solid surface is enhanced (with the adsorption energy decreasing by 33 kJ·mol

-1

)

and its activation is also promoted (COS bonds to the Ni site in the presence of H

). Furthermore

partial density of states analysis of S and Ni atoms reveals a stronger interaction between the 3p orbital of S in COS and the 3d orbital of Ni. These changes indicate that the adsorption and activation of COS on the solid surface are enhanced

which is the main reason why the Ni additives strengthen COS hydrogenolysis.

关键词

Keywords

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