Simulation study on microscopic mechanism of oriented gasification of PVC in supercritical water and its hydrogen production and dechlorination characteristics

ZHANG Peng; YU Mingshuang; LI Lei; LI Xinzhe; CUI Mao; LI Dexiang

doi:10.12434/j.issn.2097-2547.20250422

您当前的位置：

首页 >

文章列表页 >

Simulation study on microscopic mechanism of oriented gasification of PVC in supercritical water and its hydrogen production and dechlorination characteristics

更新时间：2026-06-18

- Simulation study on microscopic mechanism of oriented gasification of PVC in supercritical water and its hydrogen production and dechlorination characteristics
- Pages: 1-9(2026)
- 作者机构：
  
  1. 山东中实易通集团有限公司，山东济南 250000
  2. 山东大学核科学与能源动力学院，山东济南 250061
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20250422
  CLC： TQ32
- Received：07 November 2025，
  
  Revised：2025-12-09，
  
  Online First：18 June 2026，
- 稿件说明：
移动端阅览
张鹏,于明双,李蕾等.超临界水中PVC定向气化的微观机理及制氢与脱氯特性模拟研究[J].低碳化学与化工,

ZHANG Peng,YU Mingshuang,LI Lei,et al.Simulation study on microscopic mechanism of oriented gasification of PVC in supercritical water and its hydrogen production and dechlorination characteristics[J].Low-Carbon Chemistry and Chemical Engineering,
张鹏,于明双,李蕾等.超临界水中PVC定向气化的微观机理及制氢与脱氯特性模拟研究[J].低碳化学与化工, DOI：10.12434/j.issn.2097-2547.20250422.

ZHANG Peng,YU Mingshuang,LI Lei,et al.Simulation study on microscopic mechanism of oriented gasification of PVC in supercritical water and its hydrogen production and dechlorination characteristics[J].Low-Carbon Chemistry and Chemical Engineering, DOI：10.12434/j.issn.2097-2547.20250422.

摘要

为解决废弃PVC在传统处理过程中脱氯能耗高、易生成有毒副产物等问题，采用反应力场分子动力学（ReaxFF-MD）方法，研究了PVC在超临界水中的定向气化机理及产物调控规律。通过构建超临界水体系和蒸汽体系，揭示了体系类型、温度（2700~3300 K）和反应时间（0~1500 ps）对产物分布的影响。结果表明，相较蒸汽体系，超临界水体系能够显著加速PVC分解。温度升高有利于促进碳链断裂和脱氯反应，在3300 K时93.3%（HCl中氯与 PVC 中氯数量之比）的氯元素以HCl形式脱除，未检测到氯代烃及二噁英类副产物。反应过程表现为两个阶段：前300 ps为快速脱氯阶段，随后进入碳链深度裂解和气体产物生成阶段。超临界水体系中水分子解离产生大量·OH和·H，能够持续促进PVC链断裂，并通过自由基耦合作用及水煤气反应提高H

产率。

Abstract

To address the high dechlorination energy consumption and formation of toxic by-products in traditional treatment of waste PVC

the reaction force field molecular dynamics (ReaxFF-MD) method was employed to study the directional gasification mechanism and product regulation rules of PVC in supercritical water. By constructing supercritical water system and steam system the effects of system type

temperature (2700~3300 K) and reaction time (0~1500 ps) on product distribution were revealed. The results show that compared with the steam system

the supercritical water system can significantly enhance PVC decomposition. Increasing temperature further promotes carbon-chain cleavage and dechlorination reactions. At 3300 K

93.3% ( ratio of the amount of chlorine in HCl to that in PVC) chlorine is removed in the form of chlorine

with no chlorinated hydrocarbons or dioxin-like by-products detects. The reaction exhibits a two-stage pathway: Rapid dechlorination within the first 300 ps

followed by deep carbon-chain cracking and gas formation. In supercritical water system

dissociation of water molecules produces abundant ·OH and ·H

which accelerate PVC bond cleavage and enhance hydrogen formation through radical coupling and water-gas reactions.

关键词

Keywords

references

孙艺蕾 , 马跃 , 李术元 , 等 . 聚烯烃塑料的热解和催化热解研究进展 [J ] . 化工进展 , 2021 , 40 ( 5 ): 2784 - 2801 .

SUN Y L , MA Y , LI S Y , et al . Research progress in the pyrolysis and catalytic pyrolysis of waste polyolefin plastics [J ] . Chemical Industry and Engineering Progress , 2021 , 40 ( 5 ): 2784 - 2801 .

YAN H J , CORDIER M , UEHARA T . Future projections of global plastic pollution: Scenario analyses and policy implications [J ] . Sustainability , 2024 , 16 ( 2 ): 643 .

BHARATH M K , NATESAN U , VAIKUNTH R , et al . Spatial distribution of microplastic concentration around landfill sites and its potential risk on groundwater [J ] . Chemosphere , 2021 , 277 : 130263 .

MOUSANIA Z , ANGULO A V , POON J P H , et al . Quantifying the environmental impact of transportation for plastic film packaging end-of-life: Landfill, incineration, physical recycling, or chemical recycling [J ] . Resources, Conservation and Recycling , 2024 , 207 : 107681 .

MOHAMMADI A , MALAKOOTIAN M , DOBARADARAN S , et al . Occurrence, seasonal distribution, and ecological risk assessment of microplastics and phthalate esters in leachates of a landfill site located near the marine environment: Bushehr port, Iran as a case [J ] . Science of the Total Environment , 2022 , 842 : 156838 .

FIDA M , LI P , ALAM S M K , et al . Review of groundwater nitrate pollution from municipal landfill leachates: Implications for environmental and human health and leachate treatment technologies [J ] . Exposure and Health , 2024 , 16 ( 5 ): 1225 - 1249 .

欧振宇 , 韩俊伟 , 焦芬 , 等 . 废旧PVC电线热重分析及热解试验研究 [J ] . 甘肃科学学报 , 2023 , 35 ( 2 ): 48 - 54 .

OU Z Y , HAN J W , JIAO F , et al . Thermogravimetry analysis and pyrolysis experiment on waste PVC wires [J ] . Journal of Gansu Sciences , 2023 , 35 ( 2 ): 48 - 54 .

万东兴 , 陈玉远 , 王小飞 , 等 . 电缆组分对热稳定性影响的试验研究 [J ] . 低温建筑技术 , 2025 , 47 ( 6 ): 140 - 144 .

WAN D X , CHEN Y Y , WANG X F , et al . Experimenttal investigation of cable component eddects on thermal stability [J ] . Low Temperature Architecture Technology , 2025 , 47 ( 6 ): 140 - 144 .

CHEN Z , ZHENG Z J , HE C L , et al . Oily sludge treatment in subcritical and supercritical water: A review [J ] . Journal of Hazardous Materials , 2022 , 433 : 128761 .

WANG T T , ZHANG J Q , WANG T , et al . Current developments in multifunctional technology for waste plastic chemical recycling and case studies [J ] . International Journal of Environmental Analytical Chemistry , 2025 , 25 : 19866 .

吴爽 , 刘金宇 , 刘心好 , 等 . 生物质微波热解气化技术研究进展 [J ] . 辽宁石油化工大学学报 , 2020 , 40 ( 5 ): 22 - 27 .

WU S , LIU J Y , LIU X H , et al . Progress and outlook of microwave assisted pyrolysis in biomass gasification [J ] . Journal of Liaoning Petrochemical University , 2020 , 40 ( 5 ): 22 - 27 .

经楠楠 , 刘文红 , 李强 , 等 . PET塑料降解及其降解酶改造方法的研究进展 [J ] . 石油化工高等学校学报 , 2024 , 37 ( 1 ): 16 - 24 .

JING N N , LIU W H , LI Q , et al . Research progress of PET plastic degradation and modification methods of degrading enzymes [J ] . Journal of Petrochemical Universities , 2024 , 37 ( 1 ): 16 - 24 .

DEMIRBAS A . Pyrolysis of municipal plastic wastes for recovery of gasoline-range hydrocarbons [J ] . Journal of Analytical and Applied Pyrolysis , 2004 , 72 ( 1 ): 97 - 102 .

MISKOLCZI N , ANGYAL A , BARTHA L , et al . Fuels by pyrolysis of waste plastics from agricultural and packaging sectors in a pilot scale reactor [J ] . Fuel Processing Technology , 2009 , 90 ( 7/8 ): 1032 - 1040 .

刘旭 , 张楷文 , 张磊 , 等 . 城市生活垃圾各组分焚烧与热解行为研究 [J ] . 辽宁石油化工大学学报 , 2021 , 41 ( 5 ): 9 - 16 .

LIU X , ZHANG K W , ZHANG L , et al . Insights on the pyrolysis and waste incineration behaviors of municipal solid waste [J ] . Journal of Liaoning Petrochemical University , 2021 , 41 ( 5 ): 9 - 16 .

CHEN A X , HU R R , HAN R , et al . The production of hydrogen-rich gas from sludge steam gasification catalyzed by Ni-based sludge char prepared with mechanical ball-milling [J ] . Journal of the Energy Institute , 2021 , 99 : 21 - 30 .

HE M Y , XIAO B , HU Z Q , et al . Syngas production from catalytic gasification of waste polyethylene: Influence of temperature on gas yield and composition [J ] . International Journal of Hydrogen Energy , 2009 , 34 ( 3 ): 1342 - 1348 .

WANG C , DU M M , FENG H F , et al . Experimental investigation on biomass gasification mechanism in supercritical water for poly-generation of hydrogen-rich gas and biochar [J ] . Fuel , 2022 , 319 : 123809 .

SUN J L , FENG H F , XU J L , et al . Investigation of the conversion mechanism for hydrogen production by coal gasification in supercritical water [J ] . International Journal of Hydrogen Energy , 2021 , 46 ( 17 ): 10205 - 10215 .

TAKESHITA Y , KATO K , TAKAHASHI K , et al . Basic study on treatment of waste polyvinyl chloride plastics by hydrothermal decomposition in subcritical and supercritical regions [J ] . Journal of Supercritical Fluids , 2004 , 31 ( 2 ): 185 - 193 .

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

XUAN W W , CAO C Y , DONG Y W , et al . Exploration of the synergistic effect of co-pyrolysis of biomass and waste plastics based on ReaxFF-MD and DFT [J ] . Journal of the Energy Institute , 2023 , 111 : 101408 .

ZHANG J L , WENG X X , HAN Y , 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 .

WOOD M A , VAN DUIN A C T , STRACHAN A . Coupled thermal and electromagnetic induced decomposition in the molecular explosive α HMX; A reactive molecular dynamics study [J ] . Journal of Physical Chemistry A , 2014 , 118 ( 5 ): 885 - 895 .

CHEN J W , WANG Q T , WEI H D , et al . Molecular dynamic study on mechanisms of polyvinylidene fluoride decomposition by using supercritical water [J ] . Chemical Engineering Journal , 2022 , 431 : 133958 .

SUN H , JIN Z , YANG C , et al . COMPASS II: Extended coverage for polymer and drug-like molecule databases [J ] . Journal of Molecular Modeling , 2016 , 22 ( 2 ): 47 .

JIN H , WU Y , GUO L J , et al . Molecular dynamic investigation on hydrogen production by polycyclic aromatic hydrocarbon gasification in supercritical water [J ] . International Journal of Hydrogen Energy , 2016 , 41 ( 6 ): 3837 - 3843 .

XUAN W W , WANG H L , YAN S , et al . Exploration on the steam gasification mechanism of waste PE plastics based on ReaxFF-MD and DFT methods [J ] . Fuel , 2022 , 315 : 123121 .

LIU X Y , WANG T , CHU J C , et al . Understanding lignin gasification in supercritical water using reactive molecular dynamics simulations [J ] . Renewable Energy , 2020 , 161 : 858 - 866 .

YAN S , XIA D H , XUAN W W . New insight into enhancement effect of supercritical water on scrap tire depolymerization: A study based on ReaxFF-MD simulation and DFT method [J ] . Fuel Processing Technology , 2020 , 200 : 106309 .

BOEL M J , WANG H , AL FARRA A , et al . Hydrothermal liquefaction of plastics: A survey of the effect of reaction conditions on the reaction efficiency [J ] . Reaction Chemistry & Engineering , 2024 , 9 ( 5 ): 1014 - 1031 .

COLNIK M , KOTNIK P , KNEZ Z , et al . Degradation of polyvinyl chloride (PVC) waste with supercritical water [J ] . Processes , 2022 , 10 ( 10 ): 1940 .

POPELIER G , DOSSCHE G , KULKARNI S P , et al . A critical review of the influence of supercritical water on the pyrolysis of plastic waste: Modelling approaches and process effects [J ] . Journal of Analytical and Applied Pyrolysis , 2024 , 183 : 106805 .

任浩华 . 基于PVC热解生成HCl氯化回收LCD中的铟 [D ] . 北京 : 中国矿业大学（北京） , 2015 .

REN H H . Chlorination recovery of indium in LCD with HCl produced by PVC pyrolysis [D ] . Beijing : China University of Mining and Technology, Beijing , 2015 .

王明磊 . CaO添加下PVC热解特性及HCl脱除规律研究 [D ] . 包头 : 内蒙古科技大学 , 2022 .

WANG M L . Pyrolysis characteristics of PVC under CaO addition and HCl removal pattern under CaO [D ] . Baotou : Inner Mongolia University of Science and Technology , 2022 .

杨林月 , 张振涛 . 超临界水氧化技术处理磷酸三丁酯的实验研究 [J ] . 原子能科学技术 , 2016 , 50 ( 12 ): 2138 - 2144 .

YANG L Y , ZHANG Z T . Experiment study on treating tributyl phosphate by supercritical water oxidation [J ] . Atomic Energy Science and Technology , 2016 , 50 ( 12 ): 2138 - 2144 .

HORTON S R , WOECKENER J , MOHR R , et al . Molecular-level kinetic modeling of the gasification of common plastics [J ] . Energy & Fuels , 2016 , 30 ( 3 ): 1662 - 1674 .

Views

下载量

CNKI被引量

Alert me when the article has been cited

提交

Tools

Publicity Resources

Research progress on oxidative cracking catalysts of light alkanes to light olefins

Current status of dry reforming of methane and carbon dioxide technology and research progress of catalysts

Influence of electron interaction between Zn and Zr on performance of ZnZr catalysts for CO2 hydrogenation to methanol

Research progress on interfacial modulation of supported metal catalysts for CO2 hydrogenation to CH4/CO

Research progress of Pd-based heterogeneous catalytic system for liquid phase dehydrogenation of formic acid

Related Author

ZHANG Guoxia

HAO Pengbo

JIAO Nianming

WANG Hui

LI Xueqin

WANG Gengyi

WEI Xiao

LIU Peng

Related Institution

Beijing Key Laboratory of Ionic Liquid Clean Process, Institute of Process Engineering, Chinese Academy of Sciences

Longzihu New Energy Laboratory, Henan University, Zhengzhou Institute of Emerging Industrial Technology

Zhengzhou Institute of Emerging Industrial Technology

School of Environmental Engineering, Henan University of Technology

Institute for Carbon Neutrality, Henan University of Technology

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：464266 Visits Today：490

⁰