H2S对Pd/<italic style="font-style: italic">α</italic>-Al2O3催化剂催化草酸二甲酯合成反应性能的影响

赵立红; 梁旭; 蒋元力; 刘振峰; 谢肥东; 蔡教民; 谢进军

doi:10.12434/j.issn.2097-2547.20250071

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H₂S对Pd/α-Al₂O₃催化剂催化草酸二甲酯合成反应性能的影响

低碳分子转化合成 | 更新时间：2025-07-30

- H₂S对Pd/α-Al₂O₃催化剂催化草酸二甲酯合成反应性能的影响
- Effect of H₂S on catalytic performance of Pd/α-Al₂O₃ catalyst for synthesis of dimethyl oxalate
- 低碳化学与化工 2025, 50(7): 51-57.
- 作者机构：
  
  1.河南能源集团研究总院有限公司，河南郑州 450046
  2.郑州市绿色低碳化工能源材料工程技术研究中心，河南郑州 450046
  3.贵州黔希化工有限责任公司，贵州毕节 551500
  4.河南龙宇煤化工有限公司，河南永城 476600
  5.河南省中原大化集团有限责任公司，河南濮阳 457000
  6.山西沃能化工科技有限公司，山西临汾 041000
- 作者简介：
  
  赵立红（1981—），博士，高级工程师，研究方向为C1化学、精细化学品合成，E-mail：hncczhaolihong@163.com。
  梁旭（1981—），博士，正高级工程师，研究方向为工业催化、催化材料及膜分离技术研发，E-mail：hnecliangxu@126.com；
  蒋元力（1968—），博士，教授，研究方向为化学工程、精细化学品合成，E-mail：jyl@zzu.edu.cn。
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20250071
  中图分类号： TQ047.6;TQ426.94
- 收稿日期：2025-02-25，
  
  修回日期：2025-03-31，
  
  纸质出版日期：2025-07-25
- 稿件说明：
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赵立红,梁旭,蒋元力等.H₂S对Pd/α-Al₂O₃催化剂催化草酸二甲酯合成反应性能的影响[J].低碳化学与化工,2025,50(7):51-57.

ZHAO Lihong,LIANG Xu,JIANG Yuanli,et al.Effect of H₂S on catalytic performance of Pd/α-Al₂O₃ catalyst for synthesis of dimethyl oxalate[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(7):51-57.
赵立红,梁旭,蒋元力等.H₂S对Pd/α-Al₂O₃催化剂催化草酸二甲酯合成反应性能的影响[J].低碳化学与化工,2025,50(7):51-57. DOI： 10.12434/j.issn.2097-2547.20250071.

ZHAO Lihong,LIANG Xu,JIANG Yuanli,et al.Effect of H₂S on catalytic performance of Pd/α-Al₂O₃ catalyst for synthesis of dimethyl oxalate[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(7):51-57. DOI： 10.12434/j.issn.2097-2547.20250071.

摘要

草酸二甲酯（DMO）是合成气制乙二醇的中间产品，工业上通常采用CO和亚硝酸甲酯（MN）在Pd/

-Al

催化剂作用下制备DMO，但是在以含CO工业尾气为原料生产DMO的过程中无法避免负荷大范围波动的问题，会出现H

S等毒物含量超标情况，因此探究H

S对催化剂的毒害影响具有重要意义。采用固定床微反装置考察了H

S对利用CO和MN合成DMO的Pd/

-Al

催化剂催化性能的影响。在反应温度为120 ℃、常压、

(CO)/

(MN)为2.0以及空速为3000 h

-1

条件下，H

S毒化处理催化剂后，其MN转化率由83%降低至64%左右。对中毒处理后的催化剂进行H

还原处理，发现催化剂活性进一步降低，MN转化率稳定在51%左右。采用XRD、FT-IR、HRTEM和XPS等对新鲜催化剂、中毒处理后催化剂及H

还原处理后催化剂进行了表征分析。结果表明，H

S优先与催化剂表面Pd活性物种反应生成PdSO

、PdO

-S和PdO

-SO

等惰性物种，Pd颗粒内部仍保持Pd

状态。H

还原处理会脱除掉部分表面硫，部分氧化态Pd物种重新被还原为Pd

，但是还原处理造成Pd

颗粒团聚长大。表面PdSO

、PdO

-S和PdO

-SO

等惰性物种占据并覆盖活性中心及Pd

团聚长大是造成催化剂催化活性下降的主要原因。

Abstract

Dimethyl oxalate (DMO) is an intermediate product of syngas to ethylene glycol. In industry

DMO is typically produced via the reaction of CO and methyl nitrite (MN) over Pd/

-Al

catalyst. However

during the production of DMO using industrial tail gas

significant load fluctuations are unavoidable

and the concentration of toxic substances such as H

S may exceed permissible limits. Therefore

investigating the toxic effects of H

S on the catalyst is of critical importance. The impact of H

S on catalytic performance of the Pd/

-Al

catalyst for synthesis of DMO from CO and MN was examined using a fixed-bed microreactor. Under the temperature of 120 ℃

normal pressure

(CO)/

(MN) of 2.0

and the space velocity of 300

0 h

-1

after exposure to H

S poisoning

the conversion rate of MN decreases from 83% to about 64%. After H

reduction treatment on the poisoned catalyst

the MN conversion rate further decreases to about 51%. The structures of catalysts were characterized by XRD

FT-IR

HRTEM and XPS

etc. The results indicate that H

S preferentially reacts with palladium active species on the catalyst surface to form inert compounds such as PdSO

PdO

-S

and PdO

-SO

while the palladium particles retain Pd

state internally. H

reduction treatment removes some surface sulfur species and some oxidized Pd species are reduced back to Pd

. However

this reduction process induces the aggregation of Pd

particles. The occupation and coverage of active sites by inert species such as PdSO

PdO

-S

and PdO

-SO

along with the aggregation of Pd

are the main reasons for the decrease of cataltic activity of catalyst.

关键词

Keywords

references

郭凤钦 , 赵丽滟 , 王利国 , 等 . 草酸二甲酯催化合成高值化学品研究进展 [J ] . 洁净煤技术 , 2024 , 30 ( 2 ): 123 - 142 .

GUO F Q , ZHAO L Y , WANG L G , et al . Development and research progress of catalytic system of high-value derivatives of dimethyl oxalate [J ] . Clean Coal Technology , 2024 , 30 ( 2 ): 123 - 142 .

梁旭 , 苗杰 , 赵立红 , 等 . 一氧化碳偶联合成草酸二甲酯催化剂中试研究 [J ] . 天然气化工—C1化学与化工 , 2018 , 43 ( 6 ): 80 - 83 .

LIANG X , MIAO J , ZHAO L H , et al . Pilot test of the catalysts for synthesis of dimethyl oxalate by carbon monoxide coupling [J ] . Natural Gas Chemical Industry , 2018 , 43 ( 6 ): 80 - 83 .

梁旭 , 赵立红 , 崔发科 , 等 . 千吨级草酸二甲酯合成催化剂工业侧线试验 [J ] . 天然气化工—C1化学与化工 , 2020 , 45 ( 6 ): 51 - 57 .

LIANG X , ZHAO L H , CUI F K , et al . Industrial side-line test of catalyst for kiloton dimethyl oxalate synthesis [J ] . Natural Gas Chemical Industry , 2018 , 45 ( 6 ): 51 - 57 .

卓创咨询 . 2024 - 2025 中国乙二醇市场年度报告 [R/OL ] . 淄博 : 山东卓创资讯有限公司 , 2025-01-27 [ 2025-02-25 ] . www.sci99.com www.sci99.com .

SCI 99. COM . 2024 - 2025 China ethylene glycol market annual report [R/OL ] . Zibo : SCI 99 . COM , 2025-01-27 [ 2025-02-25 ] . www.sci99.com www.sci99.com .

WANG Z Q , SUN J , XU Z N , et al . CO direct esterification to dimethyl oxalate and dimethyl carbonate: The key functional motifs for catalytic selectivity [J ] . Nanoscale , 2020 , 12 ( 39 ): 20131 - 20140 .

WANG M L , HOU S X , YANG Y W , et al . Surface amine species promoted Cu/SiO 2 catalysts for the hydrogenation of dimethyl oxalate to ethylene glycol [J ] . Industrial & Engineering Chemistry Research , 2023 , 62 ( 27 ): 10399 - 10408 .

计扬 . CO催化偶联制草酸二甲酯反应机理、催化剂和动力学研究 [D ] . 上海 : 华东理工大学 , 2010 .

JI Y . Study of catalyst, mechanism, and intrinsic kinetics of CO catalytic coupling to dimethyl oxalate (DMO) [D ] . Shanghai : East China University of Science and Technology , 2010 .

LV D M , XU Z N , PENG S Y , et al . (Pd-CuCl 2 )/ γ -Al 2 O 3 : A high-performance catalyst for carbonylation of methyl nitrite to dimethyl carbonate [J ] . Catalysis Science & Technology , 2015 , 5 ( 6 ): 3333 - 3339 .

TAN H Z , WANG Z Q , XU Z N , et al . Active Pd(II) complexes: Enhancing catalytiv activity by ligand effect for carbonylation of methyl nitrite to dimethyl carbonate [J ] . Catalysis Science & Technology , 2017 , 7 ( 17 ): 3785 - 3790 .

潘学平 . CO偶联制草酸二甲酯反应、催化剂及其失活原因研究 [D ] . 镇江 : 江苏大学 , 2016 .

PAN X P . Study on the reaction, catalyst and deactivation of two methyl ester of oxalic acid by CO coupling [D ] . Zhenjiang : Jiangsu University , 2016 .

项铁丽 . CO偶联制草酸酯工艺条件及催化剂失活与再生研究 [D ] . 天津 : 天津大学 , 2004 .

XIANG T L . Study on technological conditions of CO coupling to oxalate and catalyst deactivation and regeneration [D ] . Tianjin : Tianjin University , 2004 .

PENG S Y , XU Z N , CHEN Q S , et al . An ultra-low Pd loading nanocatalyst with high activity and stability for CO oxidation coupling to dimethyl oxalate [J ] . Chemical Communications , 2013 , 49 ( 51 ): 5718 - 5720 .

WANG C Z , DING J , ZHAO G F , et al . Microfibers-structured Pd/AlOOH/Al-fiber for CO coupling to dimethyl oxalate: Effect of morphology of AlOOH nonosheet endogenously grown on Al-fiber [J ] . ACS Applied Materials & Interfaces , 2017 , 9 ( 11 ): 9795 - 9804 .

PENG S Y , XU Z N , CHEN Q S , et al . MgO: An excellent catalyst support for CO oxidation coupling to dimethyl oxalate [J ] . Catalysis Science & Technology , 2014 , 4 ( 7 ): 1925 - 1930 .

PENG S Y , XU Z N , CHEN Q S , et al . Enhanced stability of Pd/ZnO catalyst for CO oxidation coupling to dimethyl oxalate: Effect of Mg 2+ doping [J ] . ACS Catalysis , 2015 , 5 ( 7 ): 4410 - 4417

XIE K Y , WANG Z , JIANG B S , et al . Synthesis of quantitative sulfur-poisoned Pd/ γ -Al 2 O 3 and its deactivation mechanism for catalytic combustion of tulene [J ] . Applied Catalysis A: General , 2022 , 639 : 118641 - 118648 .

古堂生 , 林光明 . 非晶态和晶态纳米氧化铝粉的相变与红外光谱 [J ] . 无机材料学报 , 1997 , 12 ( 6 ): 840 - 844 .

GU T S , LIN G M . Phase transformation and infrared absorption spectra of amorphous and crystalline nano- Al 2 O 3 powder [J ] . Journal of Inorganic Materials , 1997 , 12 ( 6 ): 840 - 844 .

WAQIF M , BAZIN P , SAUR O , et al . Study of ceria sulfation [J ] . Applied Catalysis B: Environmental , 1997 , 11 ( 2 ): 193 - 205 .

衣启松 . 高度多孔性氧化铝材料的制备及其二氧化碳吸附性能 [D ] . 青岛 : 中国石油大学 , 2020 .

YI Q S . Preparation of highly porous alumina and application in carbon dioxide adsorption [D ] . Qingdao : China University of Petroleum , 2020 .

VÁZQUEZ A , PEDRAZA F , FUENTES S . Influence of sulfidation on the morphology and hydrodesulfurization activity of palladium particles on silica [J ] . Journal of Molecular Catalysis , 1992 , 75 ( 1 ): 63 - 70 .

HOYOS L J , PRALIAUD H , PRIMET M . Catalytic combustion of methane over palladium supported on alumina and silica in presence of hydrogen sulfide [J ] . Applied Catalysis A: General , 1993 , 98 ( 2 ): 125 - 138 .

高正虹 . CO催化偶联反应机理和杂质对催化剂活性影响研究 [D ] . 天津 : 天津大学 , 2002 .

GAO Z H . Research on the mechanism of CO-catalyzed coupling reaction and the influence of impurities on the activity of the catalyst [D ] . Tianjin : Tianjin University , 2002 .

LAMPERT J K , KAZI M S , FARRAUTO R J . Palladium catalyst performance for methane emissions abatement from lean burn natural gas vehicles [J ] . Applied Catalysis B: Environmental , 1997 , 14 ( 3/4 ): 211 - 223 .

邓友全 , 安立敦 . 担载金属催化剂硫中毒机理及其再生方法研究 I . Pd(Pt)/Al 2 O 3 催化剂 H2 -O2反应下硫中毒机理的研究[J ] . 分子催化, 1988, 2 ( 2 ): 69 - 78 .

DENG Y Q , AN L D . Study on the mechanism of sulfur poisoning and its regeneration method of metal catalysts I. Study on the mechanism of sulf poisoning of Pd(Pt)/Al 2 O 3 catalysts in H 2 -O 2 reaction [J ] . Journal of Molecular Catalysis , 1988 , 2 ( 2 ): 69 - 78 .

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H2S对Pd/α-Al2O3催化剂催化草酸二甲酯合成反应性能的影响

Effect of H2S on catalytic performance of Pd/α-Al2O3 catalyst for synthesis of dimethyl oxalate

DOI：10.12434/j.issn.2097-2547.20250071

摘要

Abstract

关键词

Keywords

references

H₂S对Pd/α-Al₂O₃催化剂催化草酸二甲酯合成反应性能的影响

Effect of H₂S on catalytic performance of Pd/α-Al₂O₃ catalyst for synthesis of dimethyl oxalate