Determination of solid-phase reaction mechanism and chlorine migration behavior of co-pyrolyzing PVCCaCO3 based polymer using temperatu... https://www.sciencedirect.

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Polymer Degradation and Stability

Volume ���, November ����, ������

Determination of solid-phase reaction mechanism and chlorine migration behavior of co-

pyrolyzing PVC CaCO3 based polymer using temperature-dependent FTIR and XRD analysis
Yanyan Zou a, Yaoqiang Li a, Serge Bourbigot b, Jiaqing Zhang c, Yi Guo c, Kaiyuan Li a , Xuanze He d , Jiayidaer Baolati a

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Abstract

This paper investigates the pyrolysis of outer sheath polymer of a PVC CaCO3 based cable. TG-DSC-MS, temperature-dependent FTIR, XRD and XPS experiments were conducted to study
the pyrolysis characteristics and chlorine migration law for solid products. The results show that the pyrolysis can be divided into three stages induced by co-pyrolysis of PVC and CaCO3. In
the first stage, the PVC dehydrohalogenation takes place producing the majority of HCl. CaCO3 does not participate in the solid-phase reaction. In the second stage, the cyclization of olefin
chains occurs with a low HCl production. The CaCO3 reacts under high temperature, absorbing HCl in crystal lattice producing CaCl2 and CO2. In the third stage, the CaCO3 continues
consuming HCl, meanwhile it starts pyrolyzing above 800 °C, generating CaO and CO2. The final residue mainly consists of CaCl2 and CaO and the organic Cl is ignorable. As the Cl-capturing
reactions occur under high temperature with a low HCl production, the efficiency of CaCO3 reducing HCl is low, which explains the findings in previous study. This paper reveals the solid-
phase reaction scheme and the law of Cl migration of the PVC CaCO3 based polymer pyrolysis, providing fundamentals for modeling and contributing to the understanding of cable
pyrolysis for incineration industry.

Introduction

As the core part of power system, the substations usually contain a large number of cables [1,2] and many of them are polymers made of flammable PVC combined with CaCO3 and other
additives [3,4]. The cables are prone to the overheating during the long-term use, causing extreme incidents such as the power failure with damaged cables and even fires. These processes
are closely related to the pyrolysis behaviors of cable materials. The outer sheath is the first and the most important protective layer of cable. Understanding the pyrolysis of the outer
sheath is of great significance for recycling and risk assessment [5,6]. Owing to the Cl element in PVC, a large amount of acidic HCl gas is produced during cable pyrolysis [7], leading to
negative effects on the environment and equipment. Therefore, how to capture Cl in the solid phase has become a hot topic in research [8]. Understanding the mechanism of solid-phase
reactions and the chlorine migration law can assist us in resolving the difficulties in capturing Cl and other potential problems.

As the main component of the outer sheath is PVC, the pyrolysis behaviors of sheath are strongly related to the PVC pyrolysis which is generally believed to follow a two-stage reaction

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Determination of solid-phase reaction mechanism and chlorine migration behavior of co-pyrolyzing PVCCaCO3 based polymer using temperatu... https://www.sciencedirect.com/science/article/abs/pii/S0141391021002615

process [7]. The first stage is the dehydrochlorination and rupture of polymer cross-linking network and the second stage is the cyclization, cross-linking and chain scission of olefins long-
chain. Zhu et al. [8] used TG-FTIR to study the pyrolysis of pure and compound PVC. It was found that the products contained a large amount of HCl and organics, and the Cl was mostly
converted into HCl, with a small number of chlorinated compounds. McNeil et al. [7] conducted Py-GC/MS experiments to identify the volatile products from PVC pyrolysis and pointed out
that the detected chlorinated hydrocarbons could be the abnormal byproducts of HCl attached to the vessel wall. The main environmental impacts of PVC CaCO3 based cable incineration
mainly come from HCl [9], [10], [11]. In the meantime, solid Cl such as poly-chlorinated dibenzo-p-dioxins and dibenzofurans could become the soil pollutants after burning [12]. Benes
et al. [13] studied the pyrolysis characteristics of PVC cables in different atmospheres and proposed that the pyrolysis of PVC skeleton produced HCl, H2O, CO2 and benzene. Wang et al. [1]
and Tang [14] used TG-FTIR to study the pyrolysis behaviors of outer sheath of PVC CaCO3 based cable and divided the pyrolysis process into two stages. Six chemical bonds were
identified in the gas products, of which the yields in descending order are CO2 > C H stretching > C H bending > C H aliphatic bending > CH2 deformation > C Cl stretching. Gong et al.
[15] studied the spontaneous combustion of flame-retardant cables and proposed that spontaneous combustion is probably caused by the smoldering of PE insulation layer. Wang et al. [4]
compared the pyrolysis behaviors of new and old sheaths and found that the new sheath pyrolyzes more easily and completely. Liu et al. [16] studied the pyrolysis kinetics and
thermodynamic parameters of PVC CaCO3 based cable sheath in an inert atmosphere. Mun et al. [17] calculated the temperature and rate of PVC CaCO3 based cable flame spread using
TG results. To improve the fire resistance of cables, a large number of heat stabilizers are added to the outer sheath, mainly CaCO3 and a small amount of Sb2O3, Al(OH)3, ZnSn(OH)6 and
B2O6Zn3, etc. These inorganic additives cannot be completely volatilized during pyrolysis and will react with PVC transforming into solid products, which affects the formation of gas
products [18]. A semi-quantitative study on the dehydrochlorination efficiency with calcium-based additives shows that the CaO has the best efficiency of capturing HCl whereas the CaCO3
has the least efficiency [8]. Three stages were identified from the pyrolysis process and it is presumed that the first and second stages correspond to PVC degradation while the third stage
corresponds to the delayed PVC degradation by additives [8]. Liu et al. [19] carried out TG analysis on the PVC composite film and showed that the nano-CaCO3 filler can improve thermal
stability. Jiang et al. [20] conducted pyrolysis experiments on the plastic wastes containing PVC and found that the CaCO3 molten salt can capture Cl, while other experiments show that the
Ca-C sorbent can capture HCl directly [21,22]. Wang et al. [23] found that the oxygen-containing functional groups generated by polycondensation with Ca forming the Ca O Ca
compounds. In addition, temperature-dependent FTIR and XRD gave strong evidences for the presences of index chemical bonds and crystals [24,25].

From the literature review, it is found that previous researches cover mainly the gas phase products [26,27], pyrolysis kinetics and combustion characteristics, little research has been
focused on the solid-phase reaction mechanism. The existing publications did not relate the Cl capturing with the solid-phase pyrolysis of PVC with detailed pyrolysis stages [28].
Therefore, there is a lack of understanding of the conversion from solid to gas phase and the formation mechanism of solid products. Moreover, most researches on cable polymers were
performed below 973 K, resulting in only two reaction stages. In fact, when the temperature approaches 900 K, the third stage of pyrolysis takes place, which has been overlooked
previously. In previous researches, the pyrolysis of PVC CaCO3 based cable has been equivalent to the PVC pyrolysis [14,16,29,30] and the final residue of cable pyrolysis is believed to be
carbon [16,[30], [31], [32]], which is not acceptable.

The current research focuses on the pyrolysis of the outer sheath polymer of ZRB-VV22–0.6/1.0 kV flame-retardant cable, of which the main components are PVC and CaCO3. Firstly, TG-
DSC-MS experiments were carried out to obtain the mass loss induced by pyrolysis and productions of indicating volatile products. Secondly, temperature-dependent FTIR experiments
were used to identify the chemical bonds in the solid products under different temperatures. Finally, the crystal distribution of residue compounds was calculated based on temperature-
dependent XRD results and the chemical form of Cl element was determined using XPS experiment. The solid-phase reaction mechanism is then generalized with the migration law of Cl
element.

Section snippets

Material

The cables were manufactured by Jiangsu Runhua Cable Co., Ltd. The model is ZRB-VV22–0.6/1.0 kV. Fig. 1a shows that the cable mainly consists of inner and outer sheaths, steel belt and
non-woven fabric, etc. The inner and outer sheaths and insulating layers are all PVC CaCO3 based materials, with slightly different in formula. The current paper focuses on the outer
sheath of which the mass fractions of C, O, Ca and Cl elements were measured using a field emission scanning electron microscope…

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Determination of solid-phase reaction mechanism and chlorine migration behavior of co-pyrolyzing PVCCaCO3 based polymer using temperatu... https://www.sciencedirect.com/science/article/abs/pii/S0141391021002615

Pyrolysis characteristics determined by TG-DSC

Fig. 2 shows the TG, derivative thermogravimetry (DTG) and DSC curves of cable outer sheath in the N2 atmosphere. According to the mass loss rate peaks in the DTG curves, the pyrolysis
process is divided into three mass loss stages of RT to 642 K, 642 K to 833 K and 833 K to 1273 K.

It can be seen in Fig. 2 that the mass loss from RT to 453 K is minor, while the mass loss gradually takes place from 453 K to 642 K, indicating that the sample has begun to pyrolyze. This is
the first pyrolysis…

Conclusions

This paper systematically studies the solid-phase reaction mechanism of the pyrolysis of PVC CaCO3 based cable outer sheath in the temperature range from RT to 1273 K, and carries out
qualitative and quantitative analysis on the pyrolysis products. Meanwhile, the migration law of Cl element during pyrolysis is studied in-depth. The TG results show that the pyrolysis of
the outer sheath has presents 3 notable mass loss periods. Therefore, the pyrolysis process is divided into three stages with…

Credit author statement

Yanyan Zou: Writing - Original Draft, Formal analysis, Writing - Review & Editing

Yaoqiang Li: Project administration, Methodology

Serge Bourbigot: Writing - Review & Editing

Jiaqing Zhang: Methodology, Project administration

Yi Guo: Investigation

Kaiyuan Li: Funding acquisition, Supervision

Xuanze He: Conceptualization, Supervision

Jiayidaer Baolati: Data Curation…

Declaration of Competing Interest

I declare there is no conflict of interest with the paper.…

Acknowledgement
This work was supported by the National Natural Science Foundation of China (NSFC) under Grant No. 51876148 and the Science and Technology Project of State Grid Anhui Electric
Corporation of China (No. 52120518001S) and Anhui Natural Science Foundation (No. 2008085UD13).…

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Determination of solid-phase reaction mechanism and chlorine migration behavior of co-pyrolyzing PVCCaCO3 based polymer using temperatu... https://www.sciencedirect.com/science/article/abs/pii/S0141391021002615

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