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

张鹏; 于明双; 李蕾; 李新哲; 崔茂; 李德祥

doi:10.12434/j.issn.2097-2547.20250422

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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

更新时间：2026-06-18

- 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
- Simulation study on microscopic mechanism of oriented gasification of PVC in supercritical water and its hydrogen production and dechlorination characteristics
- 低碳化学与化工 2026: 1-9.
- 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：
  
  张鹏（1982—），本科，高级工程师，研究方向为超临界流体技术、电站及新能源调峰调频技术，E-mail：cccpdx2@163.com。
  李德祥（1989—），博士，副研究员，硕士研究生导师，研究方向为CO2地质封存、超临界流体和气体水合物技术，E-mail：de-xiang.li@sdu.edu.cn。
- 基金信息：
  
  国家电网科研项目(ZSYT230901FWGKZB)
- DOI：10.12434/j.issn.2097-2547.20250422
  中图分类号： TQ32
- 收稿：2025-11-07，
  
  修回：2025-12-09，
  
  网络首发：2026-06-18，
- 稿件说明：
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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.

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references

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