Study on the Reaction Mechanism of Natural Rubber's Primary Pyrolysis Products

doi:10.7652/xjtuxb201901015

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Study on the Reaction Mechanism of Natural Rubber's Primary Pyrolysis Products

更新时间：2025-07-09

- Study on the Reaction Mechanism of Natural Rubber's Primary Pyrolysis Products
- Vol. 53, Issue 1, Pages: 114-121(2019)
- 作者机构：
  
  青岛大学机电工程学院,山东,青岛,266071
- 作者简介：
- 基金信息：
- DOI：10.7652/xjtuxb201901015
  CLC： TQ33
- Online First：10 January 2019，
  
  Published：2019
- 稿件说明：
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Study on the Reaction Mechanism of Natural Rubber's Primary Pyrolysis Products[J]. 2019, 53(1): 114-121.
DOI：

Study on the Reaction Mechanism of Natural Rubber's Primary Pyrolysis Products[J]. 2019, 53(1): 114-121. DOI： 10.7652/xjtuxb201901015.

摘要

针对天然橡胶初级热解(300～550 ℃)过程中的主要产物异戊二烯单体和二聚体-1

4-二甲基-4-乙烯基环己烯进一步热解生成小分子气体的生成机理展开研究

采用密度泛函理论对各个反应进行了模拟计算

得到了相关热力学参数焓变、自由能变以及动力学参数反应势垒; 用Aspen plus建立一维裂解反应器模拟实验过程

得到产物分布情况。结果表明:单体的主要反应路径为氢基与单体之间的取代反应

主要产物为氢气

反应活化能为5.68 kJ/mol

与通过热裂解工艺过程预测的产物分布结果相符; 二聚体主要通道是先发生开环反应

然后与甲基发生取代反应

主要产物为甲烷

反应活化能为354.48 kJ/mol。研究结果可为废旧轮胎的气化回收利用提供重要的理论依据。

Abstract

The generation mechanism of small molecule gas from further pyrolysis of the main products isoprene monomer and dimer-1

4-dimethyl-4-vinylcyclohexene during the primary pyrolysis(300-550 ℃)of natural rubber was studied. The density functional theory was used to simulate each reaction

and the related thermodynamic parameters of enthalpy change ΔH

free energy change ΔG

and kinetic parameter reaction barrier were obtained. The Aspen plus was used to establish a one-dimensional cracking reactor simulation experiment process to obtain product distribution. The result showed that the kinetic simulation results of the monomer were consistent with the results of the software simulation of the cracking process model. The main reaction pathway was the substitution reaction between

hydrogen radical and monomer

the main product was hydrogen

and the reaction activation energy was 5.68 kJ/mol

which were consistent with product distribution results predicted from the thermal cracking process. The main channel of the dimer was first the ring-opening reaction

and then the methyl group substitution. The main product was methane and the activation energy of the reaction was 354.48 kJ/mol. The results could provide theoretical basis for the gasification recycling of discarded tires.

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