Mechanism of effect of forming pressure on catalytic performances of Ti-Al-based COS hydrolysis catalysts

WANG Zhen; LIANG Litong; YANG Chao; FAN Huiling; CHEN Zhaohui

doi:10.12434/j.issn.2097-2547.20250195

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Mechanism of effect of forming pressure on catalytic performances of Ti-Al-based COS hydrolysis catalysts

更新时间：2026-04-23

- Mechanism of effect of forming pressure on catalytic performances of Ti-Al-based COS hydrolysis catalysts
- Vol. 51, Issue 4, Pages: 126-136(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.中国科学院过程工程研究所介科学与工程全国重点实验室，北京 100190
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20250195
  CLC： TQ426.6;TQ050.6
- Received：22 April 2025，
  
  Revised：2025-05-12，
  
  Published：25 April 2026
- 稿件说明：
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王震,梁丽彤,杨超等.成型压力对钛铝基COS水解催化剂催化性能的影响机理[J].低碳化学与化工,2026,51(4):126-136.

WANG Zhen,LIANG Litong,YANG Chao,et al.Mechanism of effect of forming pressure on catalytic performances of Ti-Al-based COS hydrolysis catalysts[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(4):126-136.
王震,梁丽彤,杨超等.成型压力对钛铝基COS水解催化剂催化性能的影响机理[J].低碳化学与化工,2026,51(4):126-136. DOI： 10.12434/j.issn.2097-2547.20250195.

WANG Zhen,LIANG Litong,YANG Chao,et al.Mechanism of effect of forming pressure on catalytic performances of Ti-Al-based COS hydrolysis catalysts[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(4):126-136. DOI： 10.12434/j.issn.2097-2547.20250195.

摘要

脱除高炉煤气中COS是钢铁行业满足超低排放要求的必要条件。目前开发的COS水解催化剂容易氧中毒失活，使用寿命短，难以满足工业应用要求。采用干混法，分别使用10 MPa、19 MPa和43 MPa 3种成型压力挤条，制备了钛铝（TiO

-Al

）基COS水解催化剂。在反应温度60 ℃、COS质量浓度300 mg/m

、O

体积分数12%和空速1000 h

-1

的条件下，对催化剂进行了催化性能测试；并采用N

吸/脱附、MIP、SEM和XPS等手段，探究了成型压力对催化剂催化性能的影响机理。结果表明，催化水解过程中，COS从催化剂外部通过孔扩散到达内部，吸附于催化剂内表面，与—OH或H

O发生水解反应生成H

S和CO

，随后H

S和CO

通过孔扩散转移至催化剂外表面。随着成型压力增大，催化剂颗粒逐渐致密化，微观上使得部分100~1000 nm大孔压缩坍塌，形成宏观上的10~360 μm超大孔，显著阻碍了COS吸附和H

S扩散；H

S吸附增多，被氧化并沉积在催化剂表面。氧空位的存在可以促进氧迁移，并在一定程度促进了COS吸附和H

S扩散，也在一定程度抑制了硫沉积。本研究可为实验室相关成果工业化转化提供参考。

Abstract

The removal of COS from blast furnace gas is essential for the steel industry to meet ultra-low emission requirements. At present

COS hydrolysis catalysts that have been developed are prone to oxygen poisoning and deactivation

have a short service life

and thus cannot meet the requirements of industrial applications. Ti-Al-based (TiO

-Al

) COS hydrolysis catalysts were prepared by a dry mixing method and extruded at forming pressures of 10 MPa

19 MPa and 43 MPa

respectively. Under the conditions of 60 ℃

COS mass concentration of 300 mg/m

volume fraction of 12% and space velocity of 1000 h

-1

the catalytic performances of the catalysts were tested. In addition

adsorption/desorption

MIP

SEM and XPS were employed to investigate the mechanism by which forming pressure affects catalytic performance. The results show that during catalytic hydrolysis

COS diffuses from the external surface of the catalyst through pores to the internal surface

where it is adsorbed and undergoes a hydrolysis reaction with —OH or H

O to produce H

S and CO

. These products then diffuse outward through the pores to the external surface of the catalyst. As the forming pressure increases

the catalyst particles become gradually densified. Microscopically

part of the 100 nm to 1000 nm macropores are compressed and collapsed

forming ultramacropores of 10 μm to 360 μm at the macroscopic scale

which significantly hinders COS adsorption and H

S diffusion. Increased H

S adsorption further leads to oxidation and sulfur deposition on the catalyst surface. The presence of oxygen vacancies ca

n promote oxygen migration

which to some extent enhances COS adsorption and facilitates the diffusion of H

thereby partially suppressing sulfur deposition. This study provides a reference for the industrial application of related laboratory research results.

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Keywords

references

陈兴业 , 向轶 , 陈艳艳 , 等 . 高炉煤气精脱硫工艺路线探究 [J ] . 中国环保产业 , 2021 , ( 3 ): 31 - 34 .

CHEN X Y , XIANG Y , CHEN Y Y , et al . Research on the process route of fine desulfurization of blast furnace gas [J ] . China Environmental Protection Industry , 2021 , ( 3 ): 31 - 34 .

中国环境保护部 . 关于发布《铁矿采选工业污染物排放标准》等8项国家污染物排放标准的公告 [EB/OL ] . ( 2012-06-27 )[ 2025-02-16 ] . https://www.mee.gov.cn/gkml/hbb/bgg/201208/t20120802_234257.htm https://www.mee.gov.cn/gkml/hbb/bgg/201208/t20120802_234257.htm .

Ministry of Environmental Protection of China . Announcement on the issuance of 8 national pollutant discharge standards including the “Emission standards for pollutants in the iron ore mining and beneficiation industry” [EB/OL ] . ( 2012-06-27 )[ 2025-02-16 ] . https://www.mee.gov.cn/gkml/hbb/bgg/201208/t20120802_234257.htm https://www.mee.gov.cn/gkml/hbb/bgg/201208/t20120802_234257.htm .

李新创 . 超低排放是中国钢铁史上的重大绿色革命解读《关于推进实施钢铁行业超低排放的意见》 [J ] . 中国钢铁业 , 2019 , ( 6 ): 9 - 11+19 .

LI X C . Extra low emission is a major green revolution in steel history [J ] . China Steel , 2019 , ( 6 ): 9 - 11+19 .

许怡 . 高炉煤气脱硫技术路径与应用研究 [J ] . 科技风 , 2020 , ( 21 ): 3 .

XU Y . Blast furnace gas desulfurization technology path and application research [J ] . Technology Wind , 2020 , ( 21 ): 3 .

GU J N , LIANG J , HU S , 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 .

CUI L , LIU M Y , YUAN X L , et al . Environmental and economic impact assessment of three sintering flue gas treatment technologies in the iron and steel industry [J ] . Journal of Cleaner Production , 2021 , 311 : 127703 .

ABOULAYT A , MAUGE F , HOGGAN P E , et al . Combined FTIR, reactivity and quantum chemistry investigation of COS hydrolysis at metal oxide surfaces used to compare hydroxyl group basicity [J ] . Catalysis Letters , 1996 , 39 : 213 - 218 .

RHODES C , RIDDEL S A , WEST J , et al . The low-temperature hydrolysis of carbonyl sulfide and carbon disulfide: A review [J ] . Catalysis Today , 2000 , 59 ( 3 ): 443 - 464 .

刘艳霞 , 上官炬 , 王泽鑫 , 等 . TiO 2 改性 γ -Al 2 O 3 基催化剂的中温水解羰基硫活性 [J ] . 化工进展 , 2018 , 37 ( 10 ): 3885 - 3894 .

LIU Y X , SHANG G J , WANG Z X , et al . Moderate temperature COS hyd rolysis activity of γ -Al 2 O 3 based catalyst modified by TiO 2 [J ] . Chemical Industry and Engineering Progress , 2018 , 37 ( 10 ): 3885 - 3894 .

李景辉 . 高含硫天然气羰基硫催化水解对气质提升与净化效率影响规律研究 [D ] . 成都 : 西南石油大学 , 2020 .

LI J H . Study on the effect of carbonyl sulfidecatalytic hydrolysis of high sulfur contentnatural gas on gas quality improvement andpurification [D ] . Chengdu : Southwest Petroleum University , 2020 .

崔明彧 , 焦建豪 , 康津铭 , 等 . 载体表面性质调控Pt-Sn/ γ -Al 2 O 3 催化剂丙烷脱氢性能 [J ] . 石油化工高等学校学报 , 2023 , 36 ( 1 ): 40 - 47 .

CUI M Y , JIAO J H , KANG J M , et al . Control of propane dehydrogenation performance of Pt-Sn/ γ -Al 2 O 3 catalysts by support surface properties [J ] . Journal of Petrochemical Universities , 2023 , 36 ( 1 ): 40 - 47 .

刘世佳 , 何凯 , 毕研峰 , 等 . γ -Al 2 O 3 载体的形貌调控及其对丙烷脱氢催化剂的影响综述 [J ] . 石油化工高等学校学报 , 2024 , 37 ( 2 ): 31 - 41 .

LIU S J , HE K , BI Y F , et al . A review of the morphological regulation of γ -Al 2 O 3 spport and its effect on propane dehydrogenation catalysts [J ] . Journal of Petrochemical Universities , 2024 , 37 ( 2 ): 31 - 41 .

SHI N , ZHU H X , QI J M , et al . Hydrolysis of carbonyl sulfide using non-ionic surfactant-modified mesoporous γ -Al 2 O 3 catalysts with high efficiency [J ] . Separation and Purification Technology , 2025 , 354 : 129356 .

JIN H K , AN Z Y , LI Q C , et al . Catalysts of ordered mesoporous alumina with a large pore size for low-temperature hydrolysis of carbonyl sulfide [J ] . Energy & Fuels , 2021 , 35 ( 10 ): 8895 - 8908 .

WU P , ZHANG Y P , LIU Y L , et al . Experimental and theoretical research on pore-modified and K-doped Al 2 O 3 catalysts for COS hydrolysis: The role of oxygen vacancies and basicity [J ] . Chemical Engineering Journal , 2022 , 450 : 138091 .

王晓玲 , 王海滨 . 高炉煤气精脱硫技术现状及未来发展展望 [J ] . 节能与环保 , 2024 , ( 7 ): 44 - 50 .

WANG X L , WANG H B . Current status and future development prospects of fine desulfurization technology for blast furnace gas [J ] . Energy Conservation & Environmental Protection , 2024 , ( 7 ): 44 - 50 .

汤雯钧 , 吕振波 , 王锐 . Boc-苯丙氨酸叔丁酯选择性脱保护工艺研究 [J ] . 辽宁石油化工大学学报 , 2024 , 44 ( 3 ): 17 - 22 .

TANG W J , LV Z B , WANG R . Study on selective deprotection process of Boc-phenylalanine tert-butyl ester [J ] . Journal of Liaoning Petrochemical University , 2024 , 44 ( 3 ): 17 - 22 .

张晓琳 , 曹志涛 , 白晓冬 , 等 . 影响助剂性能的工业化生产操作条件 [J ] . 炼油与化工 , 2024 , 35 ( 3 ): 52 - 55 .

ZHANG X L , CAO Z T , BAI X D , et al . Exploration of industrial production operating conditions that affect the performance of additives [J ] . Refining and Chemical Industry , 2024 , 35 ( 3 ): 52 - 55 .

潘瑞欣 . 高炉煤气精脱硫技术实验研究 [D ] . 西安 : 西安理工大学 , 2021 .

PAN R X . Study on fine desulfurization technology of blastfurnace gas [D ] . Xi’an : Xi’an University of Technology , 2021 .

余海清 . 苯与丙烯烷基化MCM-22分子筛催化剂的成型研究 [D ] . 北京 : 北京化工大学 , 2008 .

YU H Q . The investigation on molding condition of MCM-22 zeolite catalyst for alkylation ofbenzene with propylene [D ] . Beijing : Beijing University of Chemical Technology , 2008 .

SHEN L J , WANG G J , ZHENG X X , et al . Tuning the growth of Cu-MOFs for efficient catalytic hydrolysis of carbonyl sulfide [J ] . Chinese Journal of Catalysis , 2017 , 38 : 1373 - 1381 .

李国印 , 支建平 , 张玉林 . 表面活性剂对活性氧化铝孔结构的影响 [J ] . 日用化学工业 , 2007 , ( 3 ): 156 - 159 .

LI G Y , ZHI J P , ZHANG Y L . Influences of surfactants on pore structure in active alumina beads [J ] . China Surfactant Detergent & Cosmetics , 2007 , ( 3 ): 156 - 159 .

WANG H , XIANG J H , DENG X P . Molecular simulation of the pore structure and adsorption properties of coal under compression stress [J ] . Energy & Fuels , 2023 , 37 ( 3 ): 1887 - 1895 .

刘宏伟 , 吴慧军 , 王建设 , 等 . 挤条机结构特点与应用 [J ] . 设备管理与维修 , 2012 , ( S1 ): 116 - 117 .

LIU H W , WU H J , WANG J S , et al . Structure characteristics and application of extrusion machine [J ] . Plant Maintenance Engineering , 2012 , ( S1 ): 116 - 117 .

梁丽彤 , 上官炬 , 樊惠玲 , 等 . 高浓度COS水解催化剂抗硫中毒性能的孔隙效应 [J ] . 煤炭学报 , 2012 , 37 ( 12 ): 2102 - 2106 .

LIANG L T , SHANG G J , FAN H L , et al . Effects of pore structure on anti-sulfur poisoning of the catalyst for high concentration carbonyl sulfide hydrolysis [J ] . Journal of China Coal Society , 2012 , 37 ( 12 ): 2102 - 2106 .

李利军 . 浅析挤条机挤条困难的原因 [J ] . 当代化工 , 2004 , ( 3 ): 193 - 196 .

LI L J . Simply analysis the reason of extruder extruding piece difficulty [J ] . Contemporary Chemical Industry , 2004 , ( 3 ): 193 - 196 .

ZHANG X , TANG Y Y , QU S Q , et al . H 2 S-selective catalytic oxidation: Catalysts and processes [J ] . ACS catalysis , 2015 , 5 ( 2 ): 1053 - 1067 .

朴茜琳 , 万海 , 迟昊天 , 等 . 基于响应面法的Pt基催化剂上丙烷脱氢工艺条件优化 [J ] . 石油化工高等学校学报 , 2025 , 38 ( 2 ): 72 - 80 .

PIAO Q L , WAN H , CHI H T , et al . Optimization of propane dehydrogenation process conditions over Pt-based catalyst based on response surface methodology [J ] . Journal of Petrochemical Universities , 2025 , 38 ( 2 ): 72 - 80 .

李建伟 , 方小丽 , 李玉 . r-906催化剂上羰基硫水解反应宏观动力学 [J ] . 小氮肥设计技术 , 1996 , ( 3 ): 1 - 4 .

LI J W , FANG X L , LI Y . Macrokinetics of carbonyl sulfide hydrolysis over r-906 catalyst [J ] . Nitrogenous Fertilizer Technology , 1996 , ( 3 ): 1 - 4 .

WEN Y H , HUANG C H , ASHLEY D C , et al . Visible light-induced catalyst-free activation of peroxydisulfate: Pollutant-dependent production of reactive species [J ] . Environmental Science & Technology , 2022 , 56 : 2626 .

WEI Z , ZHANG X , ZHANG F L , et al . Boosting carbonyl sulfide catalytic hydrolysis performance over N-doped Mg-Al oxide derived from MgAl-layered double hydroxide [J ] . Journal of Hazardous Materials , 2020 , 407 : 124546 .

LIU J F , LIU Y C , XUE L , et al . Oxygen poisoning mechanism of catalytic hydrolysis of OCS over Al 2 O 3 at room temperature [J ] . Acta Physico Chimica Sinica , 2007 , 23 ( 7 ): 997 - 1002 .

屈嘉鑫 . 改性TiO 2 催化水解高炉煤气中COS和CS 2 的研究 [D ] . 昆明 : 昆明理工大学 , 2022 .

QU J X . Modified TiO 2 catalyzed hydrolysis of COS an d CS 2 in blast furnace gas [D ] . Kunming : Kunming University of Science and Technology , 2022 .

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