基于等转化率法和广义主图法的植鞣皮革热解动力学研究

doi:10.19677/j.issn.1004-7964.2022.06.002

皮革科学与工程 ›› 2022, Vol. 32 ›› Issue (6): 6-12.doi: 10.19677/j.issn.1004-7964.2022.06.002

基于等转化率法和广义主图法的植鞣皮革热解动力学研究

张铭芮¹, 王殷菲¹, 王猛¹, 王芳¹, 刘捷¹, Mădă lina Georgiana Albu Kaya², 汤克勇^1,*

1.郑州大学材料科学与工程学院,河南郑州 450001;
2.Leather and Footwear Research Institute, Collagen Department, 93 Ion Minulescu, Bucharest 031215, Romania

收稿日期:2022-05-10 出版日期:2022-12-28 上线日期:2022-11-22
通讯作者: * 汤克勇（1964-）,男,教授,主要研究方向：皮革结构与性能。E-mail:0371-67739012,kytang@zzu.edu.cn。
作者简介:张铭芮（1994-）,女,博士研究生,主要研究方向：皮革结构与性能。
基金资助:
国家自然科学基金项目（52073262,51673177）; 国家重点研发计划项目（2017YFB0308500）

Pyrolysis Kinetics of Vegetable Tanned Leather by Iso-conversional Method and Generalized Principal Diagram Method

ZHANG Mingrui¹, WANG Yinfei¹, WANG Meng¹, WANG Fang¹, LIU Jie¹, Mădă lina Georgiana Albu Kaya², TANG Keyong^1,*

1. School of Materials Science and Engineering, Zhengzhou University, Henan Zhengzhou 450001, China;
2. Leather and Footwear Research Institute, Collagen Department, 93 Ion Minulescu, Bucharest 031215, Romania

Received:2022-05-10 Online:2022-12-28 Published:2022-11-22

摘要/Abstract

摘要： 基于等转化率法和广义主图法研究了植鞣皮革的热解特性及其动力学反应模型,采用Flynn-Wall-Ozawa和Friedman两种等转化率法计算了其热解动力学参数,并根据所得结果进行模型拟合。利用热重-傅里叶变换红外光谱-质谱（TG-FTIR-MS）联用技术分析了未鞣制羊皮与植鞣皮革热解的逸出气体,讨论了未鞣制羊皮和植鞣皮革的热解特性和鉴定依据。TG-FTIR-MS分析表明,植鞣皮革受热过程中逸出的主要气体包括CH₄、NH₃、H₂O、CO、HNCO、CO₂和吡咯,CO的存在以及CH₄和NH₃强度的变化可作为皮革中鞣制与单宁的鉴定依据。广义主曲线法研究表明,植鞣皮革的热解过程遵循随机成核与核生长机理模型,不同植物鞣剂鞣制均提高了皮革的平均活化能。

关键词: 等转化率法, 广义主图法, 热解动力学, 植鞣, 活化能

Abstract: The pyrolysis characteristics and kinetic reaction models of vegetable tanned leather at three heating rates were studied based on iso-conversional method and generalized principal diagram method. Flynn-Wall-Ozawa and Friedman isoconversion method were used to calculate the pyrolysis kinetic parameters of untanned sheepskin and leathers tanned with different vegetable tanning agents. According to the results, the model was fitted. The composition of gases from the pyrolysis of vegetable tanned leather was analyzed by TG-FTIR-MS, and the pyrolysis characteristics and identification basis of vegetable tanned leather were discussed. The results showed that the main gases from vegetable-tanned leather during heating are CH₄, NH₃, H₂O, CO, HNCO, CO₂ and pyrrole. The occurrence of CO and the variation of CH₄ and NH₃ intensity could provide an identification of tannins in leathers. The generalized principal diagram showed that the pyrolysis process of vegetable tanned leather followed the random nucleation and nucleation growth mechanism model, and the average activation energy of tanned leather increased by different vegetable tanning agents.

Key words: iso-conversional method, generalized principal diagram method, pyrolysis kinetics, vegetable-tanned, activation energy

中图分类号:

TS513

张铭芮, 王殷菲, 王猛, 王芳, 刘捷, Mădă lina Georgiana Albu Kaya, 汤克勇. 基于等转化率法和广义主图法的植鞣皮革热解动力学研究[J]. 皮革科学与工程, 2022, 32(6): 6-12.

ZHANG Mingrui, WANG Yinfei, WANG Meng, WANG Fang, LIU Jie, Mădă lina Georgiana Albu Kaya, TANG Keyong. Pyrolysis Kinetics of Vegetable Tanned Leather by Iso-conversional Method and Generalized Principal Diagram Method[J]. Leather Science and Engineering, 2022, 32(6): 6-12.

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基于等转化率法和广义主图法的植鞣皮革热解动力学研究

Pyrolysis Kinetics of Vegetable Tanned Leather by Iso-conversional Method and Generalized Principal Diagram Method

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