超临界水甲烷制氢的分子动力学研究

周淑梅; 赵浩; 黄佐华; 张英佳

doi:10.7652/xjtuxb202405014

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超临界水甲烷制氢的分子动力学研究

—————————————————————— | 更新时间：2025-07-28

- 超临界水甲烷制氢的分子动力学研究
- A Molecular Dynamics Study on the Kinetic Mechanism of Methane to Hydrogen in Supercritical Water
- 西安交通大学学报 2024年58卷第5期页码：143-155
- 作者机构：
  
  西安交通大学动力工程多相流国家重点实验室,西安,710049
- 作者简介：
  
  : 2023-12-18。作者简介: 周淑梅(1999—),女,硕士生
  黄佐华(通信作者),男,教授,博士生导师。基金项目: 国家自然科学基金资助项目(51888103)。
- 基金信息：
  
  : 2023-12-18。作者简介: 周淑梅(1999—),女,硕士生;黄佐华(通信作者),男,教授,博士生导师。基金项目: 国家自然科学基金资助项目(51888103)。
- DOI：10.7652/xjtuxb202405014
  中图分类号： TK91
- 纸质出版：2024
- 稿件说明：
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周淑梅, 赵浩, 黄佐华, 等. 超临界水甲烷制氢的分子动力学研究[J]. 西安交通大学学报, 2024,58(5):143-155.

ZHOU Shumei, ZHAO Hao, HUANG Zuohua, et al. A Molecular Dynamics Study on the Kinetic Mechanism of Methane to Hydrogen in Supercritical Water[J]. 2024, 58(5): 143-155.
周淑梅, 赵浩, 黄佐华, 等. 超临界水甲烷制氢的分子动力学研究[J]. 西安交通大学学报, 2024,58(5):143-155. DOI： 10.7652/xjtuxb202405014.

ZHOU Shumei, ZHAO Hao, HUANG Zuohua, et al. A Molecular Dynamics Study on the Kinetic Mechanism of Methane to Hydrogen in Supercritical Water[J]. 2024, 58(5): 143-155. DOI： 10.7652/xjtuxb202405014.

摘要

煤-超临界水气化过程中重要中间产物挥发分的反应机理尚未明晰

采用反应分子动力学方法对重要挥发分组分甲烷(CH

)在超临界水氛围的反应机理及制氢机制进行了探究。系统比较了反应模拟时间和燃料分子规模对目标反应体系关键组分数时程和重要反应通道占比的影响

量化分析了反应温度、反应压力、CH

质量分数对超临界水相反应中CH

消耗路径和H

生成反应的影响规律。仿真结果表明

在超临界水中氧化可转化为H

、CO及少量C基中间体

O+—H〖FY〗—OH+H

是贡献H

生成的主导反应

反应过程中—OH自由基和—H原子的相对数量显著影响H

产量。降低反应温度和压力对CH

主要氧化路径影响较小

但H

净产量增加; 降低CH

质量分数

净产量先增加后减少

存在“最佳质量分数”。研究结果可为优化煤-超临界水气化过程中挥发分组分高效制氢方案提供参考。

Abstract

In order to explore the kinetic mechanism of hydrogen(H

)production in supercritical water

this study uses reactive molecular dynamics method to systematically compare the effects of simulation time and molecular number of methane(CH

)on the concentration-time evolution of key species and reaction channels

and to quantitatively analyze the multi-parameters influence on the pathways of CH

consumption and H

generation.

Results indicate that CH

can be converted into H

and CO

together with trace number of carbon-based intermediates in supercritical water. Reaction H

O+—H〖FY〗—OH+H

dominates the generation of H

during which the relative number of —OH radicals and —H atoms significantly influences the output of H

. Under the conditions investigated in this study

reduction in both temperature and pressure shows limited effect on the dominant reaction pathways during CH

consumption but presents a promotion on H

net production. Decrease in CH

mass concentration increases first and then decreases H

net production

suggesting an optimal concentration of CH

for the thermal chemistry conversion in supercritical water. The research results can provide a reference for improving the efficiency of hydrogen production of volatile components in supercritical water.

关键词

Keywords

references

SAVAGE P E. Organic chemical reactions in supercritical water [J]. Chemical Reviews, 1999, 99(2): 603-622.

AKIZUKI M, TOMITA K, OSHIMA Y. Kinetics of solid acid catalyzed 1-octene reactions with TiO2 in sub-and supercritical water [J]. The Journal of Supercritical Fluids, 2011, 56(1): 14-20.

WANG Yuzhen, GAO Fen, YANG Jianqiao, et al. Partial oxidation kinetics of the mixture of acetic acid, phenol and naphthalene in supercritical water for hydrogen production [J]. International Journal of Hydrogen Energy, 2017, 42(31): 19843-19850.

WEI Ning, XU Donghai, HAO Botian, et al. Chemical reactions of organic compounds in supercritical water gasification and oxidation [J]. Water Research, 2021, 190: 116634.

KRUSE A, DINJUS E. Hot compressed water as reaction medium and reactant: degradation reactions [J]. The Journal of Supercritical Fluids, 2007, 41(3): 361-379.

JIN Hanhui, XU Bonan, LI Hanqing, et al. Numerical investigation of coal gasification in supercritical water with the ReaxFF molecular dynamics method [J]. International Journal of Hydrogen Energy, 2018, 43(45): 20513-20524.

ZHANG Jinli, WENG Aoaoxia, HAN You, et al. The effect of supercritical water on coal pyrolysis and hydrogen production: a combined ReaxFF and DFT study [J]. Fuel, 2013, 108: 682-690.

JIANG Dandan, WANG Yan, ZHANG Ming, et al. H2 and CO production through coking wastewater in supercritical water condition: ReaxFF reactive molecular dynamics simulation [J]. International Journal of Hydrogen Energy, 2017, 42(15): 9667-9678.

JIN Hui, CHEN Bin, ZHAO Xiao, et al. Molecular dynamic simulation of hydrogen production by catalytic gasification of key intermediates of biomass in supercritical water [J]. Journal of Energy Resources Technology, 2018, 140(4): 041801.

FENG Huifang, SUN Jingli, WU Zhenqun, et al. Investigation of recycled phenol effects on supercritical water gasification of coal using ReaxFF MD simulation [J]. Fuel, 2021, 303: 121177.

FAN Mingjing, LU Youjun. Insights into carbon monoxide oxidation in supercritical H2O/CO2 mixtures using reactive molecular dynamics simulations [J]. The Journal of Supercritical Fluids, 2022, 189: 105727.

李永亮, 郭烈锦, 张明颛, 等. 高含量煤在超临界水中气化制氢的实验研究 [J]. 西安交通大学学报, 2008, 42(7): 919-924.

LI Yongliang, GUO Liejin, ZHANG Mingzhuan, et al. Hydrogen production by gasification of high concentration coal in supercritical water [J]. Journal of Xi'an Jiaotong University, 2008, 42(7): 919-924.

JIN Hui, LU Youjun, LIAO Bo, et al. Hydrogen production by coal gasification in supercritical water with a fluidized bed reactor [J]. International Journal of Hydrogen Energy, 2010, 35(13): 7151-7160.

GUO Liejin, JIN Hui, GE Zhiwei, et al. Industrialization prospects for hydrogen production by coal gasification in supercritical water and novel thermodynamic cycle power generation system with no pollution emission [J]. Science China Technological Sciences, 2015, 58(12): 1989-2002.

吕友军, 金辉, 郭烈锦, 等. 原生生物质在超临界水流化床系统中气化制氢 [J]. 西安交通大学学报, 2009, 43(2): 111-115.

LÜ Youjun, JIN Hui, GUO Liejin, et al. Hydrogen production by raw biomass gasification in supercritical water with a fluidization bed system [J]. Journal of Xi'an Jiaotong University, 2009, 43(2): 111-115.

LÜ Youjun, GUO Liejin, ZHANG Ximin, et al. Thermodynamic modeling and analysis of biomass gasification for hydrogen production in supercritical water [J]. Chemical Engineering Journal, 2007, 131(1/3): 233-244.

JIN Hui, LÜ Youjun, GUO Liejin, et al. Hydrogen production by partial oxidative gasification of biomass and its model compounds in supercritical water [J]. International Journal of Hydrogen Energy, 2010, 35(7): 3001-3010.

罗渝然. 化学键能数据手册 [M]. 北京: 科学出版社, 2005.

文玉华, 朱如曾, 周富信, 等. 分子动力学模拟的主要技术 [J]. 力学进展, 2003, 33(1): 65-73.

WEN Yuhua, ZHU Ruzeng, ZHOU Fuxin, et al. An overview on molecular dynamics simulation [J]. Advances in Mechanics, 2003, 33(1): 65-73.

VAN DUIN A C T, DASGUPTA S, LORANT F, et al. ReaxFF: a reactive force field for hydrocarbons [J]. The Journal of Physical Chemistry: A, 2001, 105(41): 9396-9409.

SENFTLE T P, HONG S, ISLAM M M, et al. The ReaxFF reactive force-field: development, applications and future directions [J]. Npj Computational Materials, 2016, 2(1): 15011.

JIN Hui, DING Weijing, BAI Bin, et al. Molecular dynamics simulation study used in systems with supercritical water [J]. Reviews in Chemical Engineering, 2022, 38(1): 95-109.

JIN Hui, WU Yue, ZHU Chao, et al. Molecular dynamic investigation on hydrogen production by furfural gasification in supercritical water [J]. International Journal of Hydrogen Energy, 2016, 41(36): 16064-16069.

WANG Tao, LIU Xiangyang, HUANG Sihan, et al. Modelling co-gasification of plastic waste and lignin in supercritical water using reactive molecular dynamics simulations [J]. International Journal of Hydrogen Energy, 2022, 47(49): 21060-21066.

CHEN Jingwei, WANG Qiteng, WEI Hongda, et al. Molecular dynamic study on mechanisms of polyvinylidene fluoride decomposition by using supercritical water [J]. Chemical Engineering Journal, 2022, 431(P1): 133958.

ASHRAF C, VAN DUIN A C T. Extension of the ReaxFF combustion force field toward syngas combustion and initial oxidation kinetics [J]. The Journal of Physical Chemistry: A, 2017, 121(5): 1051-1068.

THOMPSON A P, AKTULGA H M, BERGER R, et al. LAMMPS: a flexible simulation tool for particle-based materials modeling at the atomic, meso, and continuum scales [J]. Computer Physics Communications, 2022, 271: 108171.[28] ZHANG Yiming, LI Jialin, WANG Jianpeng, et al. ReaxFF MDSs-based studies on gasification of glucose in supercritical water under microwave heating [J]. International Journal of Hydrogen Energy, 2016, 41(31): 13390-13398.

PAYRI R, GIRALDO J S, AYYAPUREDDI S, et al. Experimental and analytical study on vapor phase and liquid penetration for a high pressure diesel injector [J]. Applied Thermal Engineering, 2018, 137: 721-728.

ZHANG Xiuxia, LIU Lining, XIAO Meihua, et al. Insight into the thermal conversion of corn stalk gasification in supercritical water based on reactive molecular dynamics simulations [J]. Journal of the Energy Institute, 2023, 106: 101156.

LI Yongliang, GUO Liejin, ZHANG Ximin, et al. Hydrogen production from coal gasification in supercritical water with a continuous flowing system [J]. International Journal of Hydrogen Energy, 2010, 35(7): 3036-3045.

JIN Hui, FAN Chao, GUO Liejin, et al. Experimental study on hydrogen production by lignite gasification in supercritical water fluidized bed reactor using external recycle of liquid residual [J]. Energy Conversion and Management, 2017, 145: 214-219.

STUKOWSKI A. Visualization and analysis of atomistic simulation data with OVITO: the open visualization tool [J]. Modelling and Simulation in Materials Science and Engineering, 2010, 18(1): 015012.

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