Suppression strategies of carbon deposit and optimization of reaction conditions for dry reforming of methane based on thermodynamic analysis

SUN Haoran; YANG Tao; LI Chao; ZHANG Meng; LIU Zhongyi; HAN Yizhuo

doi:10.12434/j.issn.2097-2547.20250176

您当前的位置：

首页 >

文章列表页 >

Suppression strategies of carbon deposit and optimization of reaction conditions for dry reforming of methane based on thermodynamic analysis

更新时间：2026-03-19

- Suppression strategies of carbon deposit and optimization of reaction conditions for dry reforming of methane based on thermodynamic analysis
- Vol. 51, Issue 3, Pages: 21-31(2026)
- 作者机构：
  
  1.郑州大学化学学院，河南郑州 450001
  2.中国科学院山西煤炭化学研究所煤炭高效低碳利用全国重点实验室，山西太原 030001
  3.中国科学院大学，北京 100049
  4.郑州大学炼焦煤资源绿色开发全国重点实验室，河南郑州 450001
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20250176
  CLC： TQ426
- Received：11 April 2025，
  
  Revised：2025-05-12，
  
  Published：25 March 2026
- 稿件说明：
移动端阅览
孙浩然,杨涛,李超等.基于热力学分析的甲烷干重整反应积炭抑制策略及反应条件优化[J].低碳化学与化工,2026,51(3):21-31.

SUN Haoran,YANG Tao,LI Chao,et al.Suppression strategies of carbon deposit and optimization of reaction conditions for dry reforming of methane based on thermodynamic analysis[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(3):21-31.
孙浩然,杨涛,李超等.基于热力学分析的甲烷干重整反应积炭抑制策略及反应条件优化[J].低碳化学与化工,2026,51(3):21-31. DOI： 10.12434/j.issn.2097-2547.20250176.

SUN Haoran,YANG Tao,LI Chao,et al.Suppression strategies of carbon deposit and optimization of reaction conditions for dry reforming of methane based on thermodynamic analysis[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(3):21-31. DOI： 10.12434/j.issn.2097-2547.20250176.

摘要

甲烷干重整（DRM）反应可以将温室气体CH

和CO

转化为高附加值的合成气，兼具环境改善与能源升级的双重效益。然而，该反应通常需要在700 ℃以上进行，能耗较高且会导致催化剂因颗粒烧结和表面积炭而失活。基于热力学分析评估了DRM反应体系的平衡组成，探讨了反应温度、惰性气体含量、反应压力和原料气进料比（

(CH

(CO

)）等对催化剂催化性能和积炭行为的影响，并对文献报道的实际反应结果与理论平衡值的偏离现象进行了深入分析。结果表明，减小

(CH

(CO

)至1:2可使原料气的完全转化温度降低200 ℃，并有效抑制反应温度700 ℃以上时的积炭生成；若

(CH

(CO

(惰性气体)调整至1:1:2也可显著抑制反应温度500~800 ℃时的积炭生成，但是适宜工业应用的高压操作不利于原料转化且会促进积炭生成。低温区（

600 ℃）和高温区（

800 ℃）的实际反应结果采用无积炭生成模型评估更为合理，而600~800 ℃区间的实际反应结果需结合积炭生成平衡模型进行评估。本研究基于热力学分析明确了DRM反应的操作边界与积炭调控策略，以期为催化剂设计与催化性能评估和优化提供重要理论依据。

Abstract

Dry reforming of methane (DRM) can convert greenhouse gases CH

and CO

into high-value syngas

with dual benefits of environmental mitigation and energy upgrading. However

this reaction usually needs to be carried out above 700 ℃

leading to high energy consumption and catalyst deactivation due to metal sintering and carbo

n deposit. The equilibrium compositions in the DRM system were systematically evaluated based on thermodynamic analysis

and the effects of reaction temperatures

inert gas contents

reaction pressures and feed ratios of raw gas (

(CH

(CO

)) on the catalytic performances and carbon deposit behaviors of catalysts were discussed. The deviations between actual reaction results reported in the literature and the theoretical equilibrium predictions were also thoroughly analyzed. The results show that reducing

(CH

(CO

) to 1:2 can lower the complete conversion temperature by 200 ℃ and effectively suppress carbon deposit formation at above 700 °C. In addition

changing the inert gas dilution ratio

(CH

(CO

(inert gas) to 1:1:2 can remarkably suppress carbon deposit from 500 ℃ to 800 ℃. However

high-pressure operations suitable for the industrial applications are not conducive to raw material conversion and can promote carbon deposit. It is more reasonable to evaluate the actual reaction results in the low-temperature zone (

600 ℃) and high-temperature zone (

800 ℃) using the no carbon deposit formation model

while the actual reaction results from 600 ℃ to 800 ℃ need to be evaluated in conjunction with the carbon deposit equilibrium model. This research clearly defines the operational boundaries and suppression strategies of carbon deposit for DRM based on thermodynamic analysis

in order to provide an essential theoretical basis for catalyst design and catalytic performance evaluation and optimization.

关键词

Keywords

references

RODHE H . A comparison of the contribution of various gases to the greenhouse effect [J ] . Science , 1990 , 248 ( 4960 ): 1217 - 1219 .

LIU Z C , YANG W M , ZHANG T . Progress in the catalytic conversion of light alkanes with carbon dioxide [J ] . SCIENTIA SINICA Chimica , 2021 , 51 ( 2 ): 154 - 164 .

SHI L , YANG G H , TAO K , et al . An introduction of CO 2 conversion by dry reforming with methane and new route of low-temperature methanol synthesis [J ] . Accounts of Chemical Research , 2013 , 46 ( 8 ): 1838 - 1847 .

JEFFRY L , ONG M Y , NOMANBHAY S , et al . Greenhouse gases utilization: A review [J ] . Fuel , 2021 , 301 : 121017 .

FU Y , SUN Y H . Challenges and prospects of CH 4 -CO 2 reforming technology [J ] . SCIENTIA SINICA Chimica , 2020 , 50 ( 7 ): 816 - 831 .

GAO X Y , LI J Y , ZHENG M D , et al . Recent progress in anti-coking Ni catalysts for thermo-catalytic conversion of greenhouse gases [J ] . Process Safety and Environmental Protection , 2021 , 156 : 598 - 616 .

PAKHARE D , SPIVEY J . A review of dry (CO 2 ) reforming of methane over noble metal catalysts [J ] . Chemical Society Reviews , 2014 , 43 ( 22 ): 7813 - 7837 .

ARORA S , PRASAD R . An overview on dry reforming of methane: Strategies to reduce carbonaceous deactivation of catalysts [J ] . RSC Advances , 2016 , 6 ( 110 ): 108668 - 108688 .

WANG Y , YAO L , WANG S H , et al . Low-temperature catalytic CO 2 dry reforming of methane on Ni-based catalysts: A review [J ] . Fuel Processing Technology , 2018 , 169 : 199 - 206 .

WANG Y , LI L , LI G Y , et al . Synergy of oxygen vacancies and Ni 0 species to promote the stability of a Ni/ZrO 2 catalyst for dry reforming of methane at low temperatures [J ] . ACS Catalysis , 2023 , 13 ( 10 ): 6486 - 6496 .

史健 , 祝星 , 李孔斋 , 等 . 甲烷干重整及金属-载体相互作用 [J ] . 石油学报（石油加工） , 2020 , 36 ( 6 ): 315 - 326 .

SHI J , ZHU X , LI K Z , et al . Dry reforming of methane and metal-support interactions [J ] . Acta Petrolei Sinica (Petroleum Processing Section) , 2020 , 36 ( 6 ): 315 - 326 .

BUELENS L C , GALVITA V V , POELMAN H , et al . Super-dry reforming of methane intensifies CO 2 utilization via Le Chatelier’s principle [J ] . Science , 2016 , 354 ( 6311 ): 449 - 452 .

ASHOK J , BIAN Z , WANG Z , et al . Ni-phyllosilicate structure derived Ni-SiO 2 -MgO catalysts for bi-reforming applications: Acidity, basicity and thermal stability [J ] . Catalysis Science & Technology , 2018 , 8 ( 6 ): 1730 - 1742 .

WEI Q H , GAO X H , WANG L H , et al . Rational design of nickel-based catalyst coupling with combined methane reforming to steadily produce syngas [J ] . Fuel , 2020 , 271 : 117631 .

CHEIN R Y , CHEN Y C , YU C T , et al . Thermodynamic analysis of dry reforming of CH 4 with CO 2 at high pressures [J ] . Journal of Natural Gas Science and Engineering , 2015 , 26 : 617 - 629 .

NIKOO M K , AMIN N A S . Thermodynamic analysis of carbon dioxide reforming of methane in view of solid carbon formation [J ] . Fuel Processing Technology , 2011 , 92 ( 3 ): 678 - 691 .

WANG N , YU X P , WANG Y , et al . A comparison study on methane dry reforming with carbon dioxide over LaNiO 3 perovskite catalysts supported on mesoporous SBA-15, MCM-41 and silica carrier [J ] . Catalysis Today , 2013 , 212 : 98 - 107 .

ARMAN A , AHAGOS F Y , ABDULLAH A , et al . Syngas production through steam and CO 2 reforming of methane over Ni-based catalyst—A review [J ] . IOP Conference Series Materials Science and Engineering , 2020 , 736 ( 4 ): 042032 .

钱慧琳 , 冉金玲 , 何安帮 , 等 . 二氧化碳-甲烷干气重整反应及其积炭控制的热力学分析 [J ] . 低碳化学与化工 , 2023 , 48 ( 5 ): 55 - 61 .

QIAN H L , RAN J L , HE A B , et al . Thermodynamic analysis of carbon dioxide methane dry gas reforming reaction and its carbon deposition control [J ] . Low-Carbon Chemistry and Chemical Engineering , 2023 , 48 ( 5 ): 55 - 61 .

WITTICH K , KRAMER M , BOTTKE N , et al . Catalytic dry reforming of methane: Insights from model systems [J ] . ChemCatChem , 2020 , 12 ( 8 ): 2130 - 2147 .

LUAN K R , ZHAO X Y , CAO J P , et al . Construction of metal-anchored and defect-rich N-doped lignite-char supported cobalt catalysts for pressurized dry reforming of methane [J ] . International Journal of Hydrogen Energy , 2024 , 82 : 600 - 610 .

LIU Q , LIU Y , ZHOU N , et al . Realization of high-pressure dry methane reforming by suppressing coke deposition with Co-Rh intermetallic clusters [J ] . Applied Catalysis B: Environmental , 2023 , 339 : 12310 .

Views

234

下载量

CNKI被引量

Alert me when the article has been cited

提交

Tools

Publicity Resources

Performance study of dry reforming of methane over three-dimensional mesoporous Ni-ZrO₂ catalysts

Process analysis of catalytic hydrogenation of CO₂ to dimethyl ether based on thermodynamic calculation

Effects of Al, Ti or Zr modification on performances of embedded Ni@SiO₂ catalysts for partial oxidation of methane to syngas

Study on dry reforming of methane catalyzed by coal char-Ni composite and electrochemical performance of formed carbon materials after reaction

Related Author

HAN Yizhuo

HUANG Lizhi

LIU Yali

WEI Qinhong

WANG Luhui

ZHENG Zeyu

CUI Lingrui

LIU Cao

Related Institution

Zhejiang Key Laboratory of Pollution Control for Port-Petrochemical Industry, Zhejiang Ocean University

National & Local Joint Engineering Research Center of Harbor Oil & Gas Storage and Transportation Technology, Zhejiang Ocean University

School of Chemical Engineering, East China University of Science and Technology

Large Industrial Reactor Engineering Research Center of the Ministry of Education, School of Chemical Engineering, East China University of Science and Technology

State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University

Postal code：610225
Tel：028-85964717 Email：236764603@qq.com
Technical support is provided by Beijing Founder electronics co., LTD 蜀ICP备12008600号-10 蜀公网安备51012202001533
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.
Total Visits：395733 Visits Today：219

⁰