Zn基高温煤气脱硫剂中Ni助剂促进COS转化作用机制

陈思思; 段新伟; 韩冰莹; 米杰; 王建成; 武蒙蒙

doi:10.11949/0438-1157.20260107

您当前的位置：

首页 >

文章列表页 >

Zn基高温煤气脱硫剂中Ni助剂促进COS转化作用机制

能源和环境工程 | 更新时间：2026-06-12

- Zn基高温煤气脱硫剂中Ni助剂促进COS转化作用机制
- Mechanism of promoting COS-conversion via Ni additives in Zn-based desulfurizers for high-temperature desulfurization of coal gas
- 化工学报 2026年
- 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：
  
  陈思思（2001—），女，硕士研究生，chensisiqwe@163.com
  武蒙蒙（1985—），男，博士，副教授，wumengmeng111@126.com, wumengmeng@tyut.edu.cn
- 基金信息：
  
  国家自然科学基金面上项目(22278294);中央引导地方科技发展资金项目(YDZJSX2025C006);山西省科技创新人才团队项目(202204051002025)
- DOI：10.11949/0438-1157.20260107
  中图分类号： TQ 546.5
- 收稿：2026-01-22，
  
  修回：2026-06-11，
  
  录用：2026-06-12，
- 稿件说明：
移动端阅览
陈思思, 段新伟, 韩冰莹, 等. Zn基高温煤气脱硫剂中Ni助剂促进COS转化作用机制[J/OL]. 化工学报, 2026.

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.
陈思思, 段新伟, 韩冰莹, 等. Zn基高温煤气脱硫剂中Ni助剂促进COS转化作用机制[J/OL]. 化工学报, 2026. DOI： 10.11949/0438-1157.20260107.

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

references

李神勇 , 秦身钧 , 门长全 , 等 . 煤基纳米功能材料的制备与应用研究进展 [J ] . 煤炭学报 , 2025 , 50 ( 7 ): 3552 - 3565 .

Li S Y , Qin S J , Men C Q , et al . Advances in preparation and application of coal-based functional nanomaterials [J ] . Journal of China Coal Society , 2025 , 50 ( 7 ): 3552 - 3565 .

Xue X J , Li Z D , Yue Y , et al . Rational construction and reaction mechanism of bimetal oxides/carbon nanofibers sorbent for H 2 S removal at high temperature [J ] . Journal of Environmental Chemical Engineering , 2025 , 13 ( 5 ): 117544 .

Li T Y , Zhu H Y , Yu Z H , et al . Promotion effects of Ni-doping on H 2 S removal and ZnO initial sulfuration over ZnO nanowire by first-principle study [J ] . Molecular Catalysis , 2022 , 519 : 112148 .

Zhao M X , Ma M Y . Investigation into the effect of adsorbed water on absorption of H 2 S in an MDEA aqueous solution enhanced by ZnO nanoparticles [J ] . ACS Omega , 2025 , 10 ( 24 ): 25938 - 25950 .

Cui Y M , Huang Y R , Mi J , et al . H 2 O-induced effects on H 2 S-absorption/COS-release behavior during hot coal gas cleaning with Zn-based sorbents and reducing its negative influence via promoter modification [J ] . Journal of Environmental Chemical Engineering , 2025 , 13 ( 5 ): 117557 .

Wu M M , Shi L , Lim T T , et al . Ordered mesoporous Zn-based supported sorbent synthesized by a new method for high-efficiency desulfurization of hot coal gas [J ] . Chemical Engineering Journal , 2018 , 353 : 273 - 287 .

Lin Y H , Chen Y C , Chu H . The mechanism of coal gas desulfurization by iron oxide sorbents [J ] . Chemosphere , 2015 , 121 : 62 - 67 .

Siam N , Guo S T , Li J F , et al . Anisotropic designing of persimmon wood-duplicated macroporous (a%Mo-Mn) 1.5 Al0.5O x and high expectative desulfurization behavior in hot coal gas [J ] . Fuel Processing Technology , 2022 , 227 : 107132 .

苏哲林 , 李敏麒 , 杨超 , 等 . Co掺杂ZnO/SiO 2 复合脱硫剂常温脱硫性能及再生性能 [J ] . 煤炭学报 , 2023 , 48 ( 10 ): 3928 - 3936 .

Su Z L , Li M Q , Yang C , et al . Desulfurization and regeneration performance of Co doped ZnO/SiO 2 composite desulfurizer at room temperature [J ] . Journal of China Coal Society , 2023 , 48 ( 10 ): 3928 - 3936 .

李俏春 , 郭恩惠 , 李阳 , 等 . 类水滑石衍生锌基复合氧化物的硫化再生行为 [J ] . 化工进展 , 2021 , 40 ( 11 ): 6278 - 6286 .

Li Q C , Guo E H , Li Y , et al . Desulfurization and regeneration behaviors of zinc-based composite oxides derived from hydrotalcite [J ] . Chemical Industry and Engineering Progress , 2021 , 40 ( 11 ): 6278 - 6286 .

Ling L X , Zhao Z B , Wang B J , et al . Effects of CO and CO 2 on the desulfurization of H 2 S using a ZnO sorbent: a density functional theory study [J ] . Physical Chemistry Chemical Physics , 2016 , 18 ( 16 ): 11150 - 11156 .

Gu J N , Liang J X , Hu S J , et al . Enhanced removal of COS from blast furnace gas via catalytic hydrolysis over Al 2 O 3 -based catalysts: Insight into the role of alkali metal hydroxide [J ] . Separation and Purification Technology , 2022 , 295 : 121356 .

张晓芬 , 邓一丹 , 段新伟 , 等 . 煤气中硫化氢和羰基硫的干法脱除/转化机理研究进展 [J ] . 低碳化学与化工 , 2025 , 50 ( 11 ): 74 - 85, 149 .

Zhang X F , Deng Y D , Duan X W , et al . Research progress on dry removal/conversion mechanisms of hydrogen sulfide and carbonyl sulfide in coal gas [J ] . Low-Carbon Chemistry and Chemical Engineering , 2025 , 50 ( 11 ): 74 - 85, 149 .

Zhao S Z , Yi H H , Tang X L , et al . The hydrolysis of carbonyl sulfide at low temperature: a review [J ] . The Scientific World Journal , 2013 , 2013 ( 1 ): 739501 .

Wu P , Zhang Y P , Wang B R , et al . Unraveling the sulfur poisoning mechanism of N-doping KAl 2 O 3 catalyst in simultaneous hydrolysis of COS and CS 2 via experimental and theoretical study [J ] . Separation and Purification Technology , 2024 , 328 : 125012 .

Li Q C , Wang X W , Zhang R , et al . Insights into the effects of metal-ion doping on the structure and hot-coal-gas desulfurization properties of Zn-based sorbents supported on SBA-15 [J ] . Fuel , 2022 , 315 : 123198 .

Huang Y R , Zhang R , Zhang M X , et al . Sheet-assembled Zn-based sorbents towards highly efficient desulfurization of hot coal gas: H 2 S-absorption/COS-release behavior and sulfur-release inhibiting mechanism [J ] . Separation and Purification Technology , 2025 , 355 : 129474 .

Deng Y D , Zhang M X , Mi J , et al . Insights into sulfur-release behavior during high-temperature desulfurization of wet coal gas via reaction-decoupling analysis and COS-formation inhibiting mechanism for doped metals [J ] . Journal of Environmental Chemical Engineering , 2025 , 13 ( 3 ): 116741 .

邓一丹 . 过渡/稀土金属助剂对锌基脱硫剂高温煤气脱硫过程中放硫行为的抑制作用 [D ] . 太原 : 太原理工大学 , 2025 .

Deng Y D . Inhibition effect of transition/rare earth metal additives on sulfur-release behavior in zinc-based desulfurizers during high-temperature coal gas desulfurization [D ] . Taiyuan : Taiyuan University of Technology , 2025 .

杨梦滋 . 高温煤气中ZnO/MCM-41脱硫过程COS生成行为及助剂改性的影响 [D ] . 太原 : 太原理工大学 , 2023 .

Yang M Z . COS formation behavior for ZnO/MCM-41 during hot coal gas desulfurization and influence of additives modification [D ] . Taiyuan : Taiyuan University of Technology , 2023 .

Zhao Y R , Zhang Z R , Yang C , et al . Critical role of water on the surface of ZnO in H 2 S removal at room temperature [J ] . Industrial & Engineering Chemistry Research , 2018 , 57 ( 45 ): 15366 - 15374 .

Yang Y M , Chen R J , Zhang Z P , et al . A 1.55 μm laser gain medium based on Yb 3+ and Er 3+ co-doped KBa 0.94 Ca 0.06 Y(MoO 4 ) 3 crystal with in-situ operating temperature self-monitoring capability [J ] . Journal of Rare Earths , 2025 , 43 ( 9 ): 1784 - 1795 .

Sun B , Zheng D L , Song X . Grand canonical Monte Carlo simulation on the metal-doped zeolite for enhancing separation of organic sulfur [J ] . Journal of Molecular Modeling , 2025 , 31 ( 9 ): 243 .

Long X H , Chen J H , Chen Y . Adsorption of ethyl xanthate on ZnS(110) surface in the presence of water molecules: a DFT study [J ] . Applied Surface Science , 2016 , 370 : 11 - 18 .

Esrafili M D . Low-temperature oxidation of methane mediated by Al-doped ZnO cluster and nanowire: a first-principles investigation [J ] . Journal of Molecular Modeling , 2024 , 30 ( 11 ): 370 .

刘磊 , 金晶 , 林郁郁 , 等 . 钙元素对焦炭表面NO吸附行为的影响: 密度泛函理论研究 [J ] . 燃料化学学报 , 2015 , 43 ( 12 ): 1414 - 1419 .

Liu L , Jin J , Lin Y Y , et al . Effect of calcium on the absorption of NO on char surface: a density functional theory study [J ] . Journal of Fuel Chemistry and Technology , 2015 , 43 ( 12 ): 1414 - 1419 .

Patwary M A , Shafin A A , Alam M M , et al . Optoelectronic properties and device simulation of ZnS polymorphs as buffer layers for CZTSSe solar cells [J ] . RSC Advances , 2025 , 15 ( 53 ): 45099 - 45111 .

Yang C Y , Rong Q Y , Shi F Y , et al . Rationally designed S-scheme heterojunction of BiOCl/g-C 3 N 4 for photodegradation of sulfamerazine: Mechanism insights, degradation pathways and DFT calculation [J ] . Chinese Chemical Letters , 2024 , 35 ( 12 ): 109767 .

Liu Y C , Chen J H , Li Y Q , et al . First-principles study on the co-adsorption of water and oxygen molecules on chalcopyrite (112)-M surface [J ] . International Journal of Mining Science and Technology , 2023 , 33 ( 8 ): 1055 - 1063 .

Chen Z J , Zheng R J , Wei W F , et al . Unlocking the electrocatalytic activity of natural chalcopyrite using mechanochemistry [J ] . Journal of Energy Chemistry , 2022 , 68 : 275 - 283 .

李敏麒 . 金属掺杂ZnO常温脱硫和再生性能研究 [D ] . 太原 : 太原理工大学 , 2021 .

Li M Q . Room temperature desulfurizers and regeneration characteristics of metal doped ZnO desulfurizer [D ] . Taiyuan : Taiyuan University of Technology , 2021 .

张丹 , 付佳 , 田虹 . Floquet变换及其在电子结构计算中的应用 [J ] . 计算数学 , 2024 , 46 ( 3 ): 385 - 396 .

Zhang D , Fu J , Tian H . Floquet transformation and its application in the calculation of electronic structures [J ] . Mathematica Numerica Sinica , 2024 , 46 ( 3 ): 385 - 396 .

Duan X W , Chen S S , Liu J W , et al . Dual-functional Zn-based sorbents for removing H 2 S from hot coal gas and suppressing COS-formation: one-pot synthesis and mechanism of inhibiting COS-release [J ] . Separation and Purification Technology , 2026 , 384 : 136350 .

Gabrienko A A , Arzumanov S S , Toktarev A V , et al . Different efficiency of Zn 2+ and ZnO species for methane activation on Zn-modifie d zeolite [J ] . ACS Catalysis , 2017 , 7 ( 3 ): 1818 - 1830 .

Li X , Wang X Q , Yuan L , et al . COS and H 2 S simultaneous removal from blast furnace gas over a tailored Cu/Zr co-doped K@TiO 2 bifunctional catalyst under low temperature [J ] . Chemical Engineering Journal , 2023 , 471 : 144573 .

Sasaoka E , Hirano S , Kasaoka S , et al . Characterization of reaction between zinc oxide and hydrogen sulfide [J ] . Energy & Fuels , 1994 , 8 ( 5 ): 1100 - 1105 .

任秀蓉 , 王海堂 , 常丽萍 . 铁基活性组分对COS的吸附及催化转化作用 [J ] . 化工进展 , 2011 , 30 ( 10 ): 2147 - 2150, 2172 .

Ren X R , Wang H T , Chang L P . Adsorption performance and catalytic conversion of iron-based active components on COS [J ] . Chemical Industry and Engineering Progress , 2011 , 30 ( 10 ): 2147 - 2150, 2172 .

Yang Y , Shi Y X , Cai N S . Simultaneous removal of COS and H 2 S from hot syngas by rare earth metal-doped SnO 2 sorbents [J ] . Fuel , 2016 , 181 : 1020 - 1026 .

Yang P , Sun Z , Duan L B , et al . Mechanism of steam-declined sulfation and steam-enhanced carbonation by DFT calculations [J ] . Greenhouse Gases: Science and Technology , 2020 , 10 ( 2 ): 472 - 483 .

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

锌基脱硫剂对高温煤气中H2S和COS共脱除行为及Mo/Ni助剂对脱硫行为的影响

［Emim］Ac-［Emim］OH-DMSO三元体系溶解纤维素的研究

酚醛树脂热裂解反应机理的密度泛函理论研究

TiAl基羰基硫水解催化剂的中毒机制与抗氧性能研究

全氟聚醚分子量及其分布表征研究