Waste Management 48 (2016) 300–314

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Review

Thermal degradation of PVC: A review

Jie Yu, Lushi Sun ⇑, Chuan Ma, Yu Qiao, Hong Yao
State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, 1037 Luoyu Road, 430074 Wuhan, Hubei, China

a r t i c l e i n f o a b s t r a c t

Article history: This review summarized various chemical recycling methods for PVC, such as pyrolysis, catalytic dechlo-
Received 28 September 2015 rination and hydrothermal treatment, with a view to solving the problem of energy crisis and the impact
Revised 16 November 2015 of environmental degradation of PVC. Emphasis was paid on the recent progress on the pyrolysis of PVC,
Accepted 24 November 2015
including co-pyrolysis of PVC with biomass/coal and other plastics, catalytic dechlorination of raw PVC or
Available online 10 December 2015
Cl-containing oil and hydrothermal treatment using subcritical and supercritical water. Understanding
the advantage and disadvantage of these treatment methods can be beneficial for treating PVC properly.
Keywords:
The dehydrochlorination of PVC mainly happed at low temperature of 250–320 °C. The process of PVC
PVC
Recycling
dehydrochlorination can catalyze and accelerate the biomass pyrolysis. The intermediates from dehy-
Co-pyrolysis drochlorination stage of PVC can increase char yield of co-pyrolysis of PVC with PP/PE/PS. For the catalytic
Catalytic pyrolysis degradation and dechlorination of PVC, metal oxides catalysts mainly acted as adsorbents for the evolved
Dechlorination HCl or as inhibitors of HCl formation depending on their basicity, while zeolites and noble metal catalysts
can produce lighter oil, depending the total number of acid sites and the number of accessible acidic sites.
For hydrothermal treatment, PVC decomposed through three stages. In the first region (T < 250 °C), PVC
went through dehydrochlorination to form polyene; in the second region (250 °C < T < 350 °C), polyene
decomposed to low-molecular weight compounds; in the third region (350 °C < T), polyene further
decomposed into a large amount of low-molecular weight compounds.
Ó 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
2. General pyrolysis mechanism of PVC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
3. Co-pyrolysis of PVC blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304
3.1. PVC/biomass waste blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304
3.2. PVC/coal blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
3.3. PVC/other plastics blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
4. Catalytic dechlorination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
4.1. Simultaneous catalytic degradation and dechlorination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
4.2. Catalytic dechlorination of oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
4.3. Separate dechlorination and catalytic degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
5. Hydrothermal treatment in supercritical or subcritical water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
6. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312

⇑ Corresponding authors.
E-mail address: sunlushi@hust.edu.cn (L. Sun).

http://dx.doi.org/10.1016/j.wasman.2015.11.041
0956-053X/Ó 2015 Elsevier Ltd. All rights reserved.
 J. Yu et al. / Waste Management 48 (2016) 300–314
1. Introduction
Plastics play an important role in our life as many objects of
daily use are made of different kinds of plastics: from packaging,
films, covers, bags and containers, to construction, electrical and
electronic applications. Of plastics, low density polyethylene
(LDPE), high density polyethylene (HDPE), polypropylene (PP),
polyvinyl chloride (PVC), polystyrene (PS) and polyethylene
terephthalate (PET) account for 74.2% of the European plastic
demand in 2012 (Fig. 1). Among these six major types of plastics,
the consumption of PVC contributes to 12% of total demand. Global
plastics production capacity for PVC was about 61 million tons in
2013. Of this, China accounted for a half (Fig. 2). The consumption
of PVC in 2013 reached 38.5 million tons. It is estimated that global
demand will rise by about 3.2%/year to 2021 (Ceresana Research,
2014). The various applications of PVC are listed in Table 1. The
biggest markets are pipes and window profiles, followed by rigid
films and cables as shown in Fig. 3. A wide range of additives are
incorporated during PVC production which can improve mechani-
cal properties of PVC products and make applications of PVC exten-
sive. Even though the durable PVC products can sustain long
service life compared with other plastics, they will eventually
become solid waste (Sadat-Shojai and Bakhshandeh, 2011).
In Europe, up to 30.8% of waste plastic was landfilled, where
plastic waste incineration with purpose of energy recovery repre-
sented the principal alternative being 39.5%. Unfortunately, only
29.7% of total plastic waste was recycled (PlasticsEurope, 2015).
Diminishing viable landfill capacity, environmental persistence
and loss of chemical/calorific value of plastics makes the landfilling
of plastic an undesirable, unsustainable option which poses a con-
siderable problem to future generations. A more suitable route is
recycling. There are mainly four types of plastic recycling and
reuse, categorised as primary (re-extrusion), secondary (mechani-
cal), tertiary (chemical recycling) as well as quaternary recycling
(energy recovery) as shown in Fig. 4 (Goodman, 2014). The type
of recycling used is dependent upon a number of factors, varying
from location, to physical and chemical requirements. Primary
recycling is the technique whereby waste plastic polymers of a
single type or origin, are reintroduced into the extrusion cycle to
Fig. 1. European plastic demand by category (PlasticsEurope, 2013) (date: 2012).
Fig. 2. Distribution of global PVC production, by region (Attenberger et al., 2014)
(date 2013: 61 million tons).
301
produce similar materials or products. Plastics found in municipal
solid waste are often not suitable for use in the primary recycling
process due to contamination. Energy recovery, mainly incinera-
tion, is highly controversial due to the formation of toxic pollutants
such as SO2, NOx, heavy metals and particulates in both flue gas
and solid residues even though it can reduce the volume and pro-
duce energy. Secondary recycling, also known as mechanical recy-
cling, is a preferable way only if sufficient quantities of
homogeneous and source-separated waste can be prepared. The
inhomogeneity of municipal solid waste makes it very difficult to
be recycled (Sadat-Shojai and Bakhshandeh, 2011). Among all the
four methods of recycling, only chemical recycling conforms to
the principles of sustainable development because it leads to the
formation of the raw materials from which the plastics are origi-
nally made. Therefore, chemical recycling is increasingly gaining
the attention of more researchers. Chemical recycling refers to
the use of advanced technologies to convert plastic materials by
depolymerisation to smaller units either in the form of monomers
or partial degradation to secondary valuable materials. Chemical
recycling can be classified as cracking/pyrolysis, gasification and
chemical depolymerisation. One usual approach for chemical recy-
cling of PVC wastes is cracking/pyrolysis including hydrocracking,
thermal cracking and catalytic cracking (Goodman, 2014). Gasifica-
tion is also used to produce a mixture of hydrocarbons and synthe-
sis gas (CO and H2), which has advantages over the normal process
of combustion due to some of the calorific value being derived
Table 1
Overview of the major applications of PVC (Keane, 2007).
General Specific examples
application
Construction Window frames and doors; Potable and gravity pipes;
Gutterings; Cables ducting and conduits; Flooring; Wall
coverings; Reservoir linings; Sheets and panels; Roller
shutters; Sports stadium seats
Medical Pharmaceutical blisters; Blood bags; Plasma bags;
Tubing; Infusion kits
Electrical Keyboards; Computers; Power tools; Electrical cords;
Phone systems; Cellular phones; Component housings
Automobile Interior trims (sun visors handbrake and gearbox lever
parts carpets etc.); Window encapsulation; Dashboard
skins; Coated fabrics (seat coatings door panels etc.);
Wire harness systems (cable sheaths grommets etc.);
Sealant (underbody insulation etc.)
Packaging Food packaging (thermoformed cups); Mineral water
bottles; Cling films; Non-food packaging (trays
cosmetics and detergents containers etc.); Bottle caps
Cards Credit cards; Smart cards; Identity cards; Telephone
cards
Leisure and sports Toys; Footballs; Swimming rings; Garden hoses;
Liferafts; Ship construction
Office Office supplies (folders ring binders rulers etc.);
Computer cases; Computer keyboards; Printing
applications
Clothing Raincoats; Lifevests; Shoe soles; Rubber boots;
Imitation leather
Fig. 3. PVC application worldwide (Attenberger et al., 2014) (date 2013: 38.5
million tons).
302 J. Yu et al. / Waste Management 48 (2016) 300–314

Primary
Re-extrusion
Recycling

Gasificaon

Hydrocracking
Plasc Waste Terary Pyrolysis Thermal cracking
Management Recycling
Catalytic Cracking

Chemical
Depolymerisaon

Secondary Mechanical
Recycling recycling

Fig. 4. Different method of PVC recycling (Sadat-Shojai and Bakhshandeh, 2011; Goodman, 2014).

from the plastic as heat and also useful fuels/chemical intermedi-

ates. Moreover, it can reduce the production of detrimental gases,
such as light hydrocarbons, nitrous oxides, sulphur oxides and
dioxins (Al-Salem et al., 2010). This review mainly focuses on the
chemical recycling of PVC by means of cracking/pyrolysis and
hydrothermal treatment.

2. General pyrolysis mechanism of PVC

As shown in Fig. 5, the onset temperature of PVC decomposition

is much lower than those of other plastics. It was proposed that the
low stability can be attributed to the presence of thermally labile
structural segments or defects of the polymer chains (Starnes Jr.,
2002; Sánchez-Jiménez et al., 2010). Various labile struc-
tural defects have been suggested to explain the low stability of
PVC. Martínez et al. (1993) claimed the GTTG (G = gauche,
T = trans) isotactic triad conformation was responsible of the ther-
mal instability. According to Béla, 1996, the initiation of PVC
decomposition was due to the random allylic chlorine atoms or Fig. 5. Analysis of the PE (Matsuzawa et al., 2004), PP (Matsuzawa et al., 2004), PET
(Martı´n-Gullón et al., 2001), PS (Matsuzawa et al., 2004) and PVC (Matsuzawa et al.,
branches with tertiary chlorine atoms. Minsker (1994) proposed
2004) pyrolysis at 10 K min 1.
that ketoallylic chlorine atoms ACO(CH@CH)nCHClA (n P 1)
resulting from incidental air oxidation played a role in low stability
of PVC. Other defect structures, such as internal double bond
Table 2
(Braun et al., 1981) and head-to-head structure (Crawley and
Major additives for PVC polymer (Shashoua and Nationalmuseet, 2001).
McNeill, 1978), have also been proposed to explain the instability
of PVC. Even though there is still no consensus on the cause of ther- Additives Major function Example

mal instability of PVC, internal allylic and tertiary chloride seg- Plasticizer Soften PVC Phthalate esters; Aliphatic diesters;
ments is considered to be of prime importance (Bacaloglu and Reduce Tg Epoxidzed oils; Phosphate esters;
Polyesters
Fisch, 1994; Starnes Jr, 2002). Different with HDPE, LDPE, PS and
PP, which have been categorized to one group with one-stage Stabilizer Minimise or eliminate Tin mercaptides; Barium-cadmium;
degrading Salts of fatty acids; Lead salts; Alkyl
decomposition reaction, pyrolysis of PVC is characteristic of two
Effects of heat, light or benzenes; Epoxidized soya; Bean oil
distinct stages. According to López et al. (2011), the main mass loss oxygen on PVC
of PVC was between 250 and 320 °C, depending on the material
Lubricant Prevent adhesion of Calcium stearate; Normal and
and the stabilizers and additives. Generally, the first stage occurs compound to Processing dibasic; Lead stearate
in the temperature range approximate 250–350 °C with a weight equipment
loss of approximate 65%. In this stage, the main reaction is the Filler Opacify compound Calcium carbonate
dehydrochlorination of the polymer forming de-HCl PVC and increase hardness Magnesium
volatiles (Jordan et al., 2001). The volatiles mainly consist of HCl, Reduce cost Carbonate
Barium sulphate
small amounts of benzene, toluene and other hydrocarbons. After
this stage, chlorine was nearly completely removed. It means that
at low temperature most chlorine can be removed from PVC, which
is the basis of further processes for the treatment of PVC. The Marcilla and Beltrán (1995) revealed that the PVC decomposition
second stage extending from 350 to 525 °C corresponds to the took place in three consecutive processes: (1) conversion of PVC
cracking and decomposition of the de-HCl PVC. into intermediates and HCl; (2) decomposition of intermediate into
Different model has been developed to explain the mechanism polyene chain and other volatiles; and (3) decomposition of poly-
of PVC decomposition. A series reaction model proposed by ene into toluene (and other aromatics) and chars. However,
 J. Yu et al. / Waste Management 48 (2016) 300–314 303

Table 3
Comparison of modified LDH effect on PVC pyrolysis behavior.

Zhu et al. (2011) MgCuAl-LDH MgCuAl-LDH increased the thermal stability time of PVC composites by 50% but decreased the 40% weight
loss temperature by about 20 °C in both N2 and air, compared with MgAl-LDH
Yi et al. (2011) MgAlCe-LDHs The PVC composites containing MgAlCe-LDHs only showed a better thermal stability, when the amount of
MgAlCe–LDH filler was 3 parts per hundred PVC resin and the molar ratio of Ce/Al was 0.075
Liu et al. (2015) Sb-LDH Sb-LDH showed limited thermal stability for PVC at the early stage of thermal and thermooxidative
degradation processes. However, Sb-LDH could retard the thermal cracking of the carbonaceous
conjugated polyene of PVC which may hinder further degradation
Labuschagne et al. MgFeAl-LDH, CaAl-LDH, The ranking of the additives from fastest to slowest degrading was as follows: MgFeAl-LDH  CaAl-
(2015) MgCuAl-LDH, MgZnAl-LDH LDH > MgCuAl–LDH  MgZnAl-LDH  MgAl–LDH, whereas the ranking of the additives with respect to
MgAl-LDH the Metrastat heat stability times was (from fastest to slowest degrading): MgAl-LDH > MgCuAl–
LDH  CaAl-LDH  MgFeAl-LDH  MgZnAl–LDH. The best performance in dynamic heat stability tests
was achieved with the conventional MgAl-LDH. However, MgZnAl–LDH improved colour retention in
Metrastat static heat stability tests. In addition, MgCuAl–LDH performed better as an HCl scavenger,
preventing the release of hydrochloric acid for a longer time in the Thermomat evaluation. The results
showed that the effect of different modified LDH varied in terms of different purpose
Gu et al. (2010) PVC/ZnMgAl–LDH-stearate PVC/ZnMgAl–LDH-stearate nanocomposites had much more thermal stability time than PVC and PVC/
nanocomposites ZnMgAl–LDH composites
Gupta et al. (2012) Ca–Al–LDH Ca–Al–LDH showed comparable stability behavior with MgAl-LDH, whereas HCl scavenging ability of
MgAl–LDH LiAl–LDH followed the order Li–Al–Cl > Li–Al–CO3 > Li–Al–SO4 > Li–Al–NO3. Modifications of LDHs
Li–Al–LDH through partial or full substitution of the magnesium or aluminium components of conventional LDH with
other metals depended on the metals used. Different metal substitutions affected performance differently
in different heat stability tests, indicating that there should be room for fine tuning of LDH heat stabilisers
for optimal performance in specific tests and end-use applications. Moreover, anions seems to be playing a
higher effect than metals

Sánchez-Jiménez et al. (2010) proposed that the PVC dehydrochlo-
rination stage involved two different chlorine groups and sug-
gested a different kinetic model for two different chlorine
groups: the first one involved a nucleation and growth model,
which dominated in lower temperature range, whereas the second
one involved a diffusion controlled model in higher temperature
range. Wu et al. (1994a,b) also found the existence of two inflex-
ional points in the first stage and proposed that the first stage
was really made up of two independent decomposition processes
related to the existence of different configurations in the polymer
chains with different thermal stabilities (head-to-head and head-
to-tail configurations), while the second stage may consist of two
competitive reactions. Existence of a no decomposition zone (flat
region) after the first stage was highlighted by Kim (2001) suggest-
ing that the intermediate went through arrangement after comple-
tion of their generation. The generation of intermediates was
followed by their decomposition reaction independently. The con-
version of intermediates produced after dehydrochlorination is of
importance to obtain the desired products. A model of two com-
petitive reaction of intermediate decomposition was proposed by
Wu et al. (1994a,b), which gave good agreement with the TG
experimental results. A four regions degradation mechanism were
proposed by Jordan et al. (2001) to explain the decomposition of
de-HCl PVC (intermediates) based on the analysis using TGA: (1)
final stage of de-HCl; (2) random chain scission with subsequent
recombination; (3) cyclization/aromatization; (4) degradation
from coke formation. Based on a wire-mesh reactor minimizing
inter-particle secondary reaction of the volatiles, Gui et al. (2013)
proposed a new four-stage mechanism of the PVC tar formation:
(1) dechlorination accompanied with inner cyclization; (2) aro-
matic chain scission; (3) release of quasi-3 rings or 3 rings group;
and (4) release of 2 rings group. In order to clearly understand
mechanism of PVC decomposition, a mechanistic model including
40 species and 250 reactions capable of accounting for the differ-
ences in starting material and be able to describe the reaction pro-
cess over a wide range of heating rates and temperatures was
developed by Marongiu et al. (2003). This model can adapt to a
wider range of experimental conditions and can predict product
distribution.
In the presence of HCl, PVC decomposition proceeds as an auto-
catalytic decomposition of the PVC backbone with the liberated
HCl assuming a catalytic role (Starnes Jr, 2002; Starnes and Ge,
2004). Troitskii et al. (1973) proposed the accelerating effect of
HCl on the thermal dehydrochlorination of PVC by molecular, ionic,
and radical mechanism. In the thermal treatment of PVC with con-
tinuous and effective removal of HCl from the reaction zone, auto-
catalysis can be hindered (Troitskii et al., 1978). In order to stop
autocatalytic dehydrochlorination of PVC, enhance their stability
or to modify their end-use properties and product performance,
additives are added into pure PVC. The PVC additives can be clas-
sified as follows: stabilizer, plasticizers, lubricants, colorant, filler,
impact modifier, flame retardants, antistatic agents and blowing
agents (Deanin, 1975; Møller et al., 1995). The amount of additives
may reach 70% of the total mass (Zaikov et al., 2000). The additives,
such as metals, metal oxides, metal chlorides, metal hydroxides,
metal carboxylates, calcium carbonate, and clay materials (Xu
et al., 2006), could accelerate or hinder the dehydrochlorination
reaction stage (Beltrán and Marcilla, 1997; Marcilla and Beltrán,
1997, 1998; McNeill et al., 1998; Blazsó and Jakab, 1999; Wang,
2000; Kalouskova et al., 2004; Saeed et al., 2004b). Therefore, the
mechanism of pure PVC resins decomposition may fail to explain
pyrolysis behavior of PVC waste due to existence of a variety of
additives. Table 2 showed the major additives of PVC and major
chemical compounds for each additive.
Stabilizers are the most important category of additives, which
could be classified as lead-based stabilizers, mixed metal stabilizers
(for example Ca/Zn, Ba/Zn, etc), tin-based stabilizers and organic
stabilizers (Markarian, 2007). In order to study the effect of stabiliz-
ers on PVC decomposition, extensive works have been performed.
For example, a stabilizer (dioctylyin maleate), can retard the dehy-
drochlorination as a result of interaction with either the HCl formed
or the active chlorine atom or with both (McNeill et al., 1998). Other
stabilizers, barium-zinc carboxylate and octadecyl-3-(3,5-tert-but
yl-hydroxyphenyl)-propionate, rarely retarded (Jiménez et al.,
1997). Fedorov et al. (2008) summarized the effect of various
inorganic additives (metals oxides, chlorides and carbonates) on
the process of hydrochlorination and pyrolysis of PVC. Generally, a
decrease in temperature of the PVC dehydrochlorination step was
304 J. Yu et al. / Waste Management 48 (2016) 300–314
noted in the presence of chromium, iron, cobalt, copper and molyb-
denum oxides. Aluminium, titanium, circonium, cerium and lead
oxides did not change onset temperature of PVC destruction. No
effect the oxides was noted at the second step of PVC destruction.
Considering environmental impact, heavy metal-based stabilisers
are being phased out. Layered double hydroxides (LDH) are proved
as promising alternatives for heavy metal-based stabilisers owing
to their intrinsically high capacity to react with HCl (Labuschagne
et al., 2015). LDH is a non-toxic, environmentally friendly layered
inorganic material, having a stacking of positively charged octahe-
dral sheets with [MII1 xMIIIx(OH)2]x+(An( x/n))
mH2O composition,
wherein MII, MIII, and A represent divalent (or monovalent) cation
(e.g. Ca2+, Mg2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+ or Zn2+), trivalent cation
(e.g. Al3+), and the interlayer anion (e.g. Cl , Br , NO3 , CO23 , SO24
and SeO24 ), respectively. Unlike most metallic salts, the LDH is readily
incorporated into the PVC resin to provide translucent articles (Liu
et al., 2007).
Van der Ven et al. (2000) hypothesized three possibilities to
explain the HCl adsorption by LDH: 1. With the anion, e.g. CO23
or OH located as counterion between the cationic LDH layers; 2.
With the LDH layers only; 3. With both the LDH layers and the
counterions between the layers. The authors measured the capac-
ity of LDH with the same M2+/M3+ ratio and different counter-ions
to react with HCl gas. A linear correlation between increasing HCl
capacity and thermal stability of the LDH in the order SO24
< Cl < OH < NO3 < CO23 < C17H35COO was found. They sug-
gested that the reaction between the LDH and HCl generally
occurred in a two step-process: firstly, the interlayer anions react
with HCl gas and secondly, the LDH layers themselves reacted with
HCl, leaching to a complete destruction of LDH structure and for-
mation of metal chlorides. Wang and Zhang (2004) studied the
effect of LDH on decomposition of PVC and found that the thermal
stability of PVC was improved remarkably by LDH, which was attri-
butable to the stabilizing mechanisms that the electrostatic inter-
action, generated between the electron cloud of chlorine atoms in
PVC chain and the positive layer charge of hydrotalcite, resulted in
a decrease in electronic cloud density of chlorine atoms. This weak-
ened the activity of chloride atoms, and restricted the initiation of
the dehydrochlorination. Lin et al. (2005) studied the effect of vary-
ing composition, structure and added amounts of Mg–Al–CO3 LDH
on the thermal stability of PVC. It was found that the charge den-
sity of the layers in Mg–Al–CO3 LDHs decreased with increasing
Mg/Al molar ratio, leading to weaker electrostatic attraction
between the layers and interlayer anions and consequently a
reduced driving force for entry of Cl into the interlayer galleries.
Liu et al. (2008) prepared PVC/ LDH nanocomposites via solution
intercalation process using organo-LDH with NO3 , dodecyl
sulphate (DS ) or stearate anions in the interlayer space. The
PVC/LDH-DS nanocomposite exhibited obviously enhanced ther-
mal stability relative to the neat PVC resin and the PVC/LDH-NO3
composite. More importantly, the nanocomposite containing Mg3-
Al-LDH-stearate showed a further significant increase of thermal
stability and dehydrochlorination time compared to PVC/LDH-DS
nanocomposites, because the interlayer stearate anions have the
intrinsic HCl absorption ability. It can be inferred that the first step
that the interlayer anions reacted with HCl gas played a significant
effect on stability of PVC.
The modifications of LDH, which is related to partial or full sub-
stitution of the magnesium or aluminium components of conven-
tional LDH with other metals, on the heat stability of plasticised
PVC was proposed recently. Novel LDH, such as MgCuAl–LDH
(Zhu et al., 2011; Labuschagne et al., 2015), MgFeAl–LDH
(Labuschagne et al., 2015), MgZnAl–LDH (Gu et al., 2010; Wang
et al., 2013; Labuschagne et al., 2015), MgCeAl–LDH (Yi et al.,
2011), MgSnAl–LDH (Zheng and Cusack, 2013), MgSbAl–LDH (Liu
et al., 2015), ZnAl–LDH (Wen et al., 2012), LiAl–LDH (Gupta et al.,
2012) and CaAl–LDH (Labuschagne et al., 2015; Wen et al., 2015)
were studied. The effect of different modified LDH additives on
PVC pyrolysis behavior are summarized and compared in Table 3.
3. Co-pyrolysis of PVC blends
A steadily increasing proportion of plastic materials gradually
entered the waste as greater numbers of PVC products approach
to the end of their useful economic lives (Sadat-Shojai and
Bakhshandeh, 2011). Recycling of plastics which can recovery
energy and/or material content without any special environment
problems has aroused interest of many researchers
(Subramanian, 2000; Al-Salem et al., 2009; Sadat-Shojai and
Bakhshandeh, 2011). Despite the advantage of recycling, however,
it is still a challenge to recycle all plastics from waste stream tech-
nically and economically. Moreover, many types of plastics cannot
simply be separated from each other (Garcia et al., 2007; Park et al.,
2007). When plastics is co-pyrolyzed with other type of waste, the
route of plastics pyrolysis can be changed due to the interactions.
For example, for mixtures of PVC with rice, poplar wood, tissue
paper, or rubber powder, higher char yields were achieved, while
the char yield was decreased when PVC was co-pyrolyzed with
wool (Zhou et al., 2015b). Therefore, in order to require a proper
understanding of the thermal properties and reaction process of
waste mixtures, the co-pyrolysis of plastic with different wastes
has been extensively studied. The application of co-pyrolysis tech-
nologies also need the understanding of interaction between dif-
ferent wastes. The key of co-pyrolysis mainly is the synergistic
effect which comes from the reaction of different materials during
the pyrolysis. Many researchers have studied the co-pyrolysis of
plastic with other plastics or biomass/coal. Therefore, the co-
pyrolysis of PVC with other plastics and biomass/coal is summa-
rized in this part.
3.1. PVC/biomass waste blends
Biomass is mainly composed of cellulose, hemicellulose and lig-
nin. Among these three major components of biomass, hemicellu-
lose decomposes between 200 and 350 °C, whereas cellulose
decomposes from 305 to 375 °C and pyrolysis of lignin mainly hap-
pens in a wide temperature range of 160 to 500 °C (Yang et al.,
2007). The TG analysis of different types of biomass also shows
that biomass pyrolysis mainly happened between 200 and 500 °C
(Părpăritßă et al., 2014). The temperature range of PVC pyrolysis is
close to that of biomass. For biomass and PVC mixtures, the DTG
curves show clearly two major steps (Aboulkas and El Harfi,
2009). The first step, obtained in the temperature range
(420–685 K), is attributed to the decomposition of hemicelluloses,
cellulose and dehydrochlorination of PVC, whereas the second step
occurs between 631 and 840 K, which corresponds to the decom-
position of de-HCl PVC and lignin. The overlap of pyrolysis temper-
ature increases the likelihood of interaction between PVC and
biomass.
TG analysis proves to be a good tool to study the thermal beha-
vior during the pyrolysis of fuel by comparing the TG/DTG curves
between experimental and predicted curves. Munther et al.
(2010) studied the co-pyrolysis of PVC with biomass in TG and
found that the two expected peaks combined into a single peak
indicating a strong interaction between PVC with biomass.
Aboulkas and El Harfi (2009) found that PVC in a mixture decom-
posed at higher temperatures than pure PVC, while the olive
residue in a mixture degrades at the lower temperatures than pure
olive residue. Sørum et al. (2001) also found the similar phe-
nomenon for co-pyrolysis of PVC with newspaper (mainly cellu-
lose) in TG. In this study, a significant interaction was observed
 J. Yu et al. / Waste Management 48 (2016) 300–314
in the first stage of decomposition, while the second stage of
decomposition (degradation of hydrocarbons in PVC) was hardly
affected. The first stage of newspaper pyrolysis can be accelerated
by the dehydrochlorination of PVC: the sum of the single compo-
nents conversion was 40 wt.% at 325 °C, while the conversion of
the mixture reached 55 wt.%. It seems that the dehydrochlorina-
tion of PVC can accelerate the biomass pyrolysis at low tempera-
ture range. Similarly, Zhou et al. (2015a) found that the
interaction of tissue paper and PVC promoted pyrolysis at low tem-
perature and suppressed the pyrolysis at high temperature, which
increased char yield. It was also found by TG-FTIR that the second
and third peaks of HCl disappeared due to the interaction.
Cellulose, hemicellulose and lignin are three major constituents.
The interaction must be related to cellulose, hemicellulose or lig-
nin. The cellulose is principal constituent in biomass, which
accounts for approximate 40–60%. The study of co-pyrolysis of
PVC with cellulose can help understanding the interaction between
PVC and biomass. This was supported by Matsuzawa et al. (2001).
They found the degradation of a mixture containing only 2 wt.%
PVC is significant different from that of pure cellulose. PVC in a
mixture degraded at higher temperature than pure PV, whereas
cellulose in the mixtures degraded at the lower temperature than
pure cellulose. HCl evolution from PVC may possibly function as
acid-catalyst for the dehydration and decomposition of the
glucose-monomers of the cellulose.
The phenomenon of higher char yields has also been observed
for co-pyrolysis of PVC with biomass by other researchers.
McGhee et al. (1995) pyrolyzed mixtures of PVC with straw and
the individual components in tube furnace. A higher amount of
chars was obtained. Moreover, the combustion reactivity of chars
produced from mixtures of straw with PVC were significantly
lower than that expected if the individual components were pyrol-
ysed separately. Munther et al. (2010) pyrolyzed a mixture of PVC
with wood in TG. An increase in final weight of 2.5% was obtained
compared with predicted one. Aboulkas and El Harfi (2009) per-
formed co-pyrolysis of PVC with olive residue and also obtained
higher char yields for mixtures. Han et al. (2014) studied the co-
pyrolysis behaviors of PVC with pine wood blends in TG. The
experimental char yield increased by approximately 10% for mix-
tures compared with predicted one. Zhou et al. (2015c) found the
pyrolysis of mixture of PVC with cellulose behaved differently with
mixtures of PVC with xylan or lignin in terms of gas and char
yields. Char yield decreased for the mixture of PVC with xylan or
lignin and gas yield increased, whereas the mixture of PVC with
cellulose showed an opposite trend. The author suggested that
the xylan or lignin served as a catalyst inhibiting the dehydrochlo-
rination process or promoting the chain scission of PVC. Therefore,
the increased char yield during co-pyrolysis of PVC with biomass
may be caused by cellulose.
For co-pyrolysis of cellulose with PVC, the amount of residual
char obtained from experiment was found higher than predicated
one (Matsuzawa et al., 2001, 2004), which may partially explain
the increased char yields for co-pyrolysis of PVC with biomass. Cel-
lulose pyrolysis occurs mainly in two competing reactions: (1)
Dehydration and charring, (2) Transglycosylation and levoglucosan
formation. HCl evolution from PVC at lower temperature can cause
dehydration of cellulose and increase the production of aldehyde
from cellulose. Dehydration at lower temperature diminished
hydrogen and oxygen atoms in cellulose and the production of
aldehyde at lower temperature was indication of the leavage of
glycosidic units, which reduced the chance of depolymerization
and amount of tar, such as levoglucosan. The lack of hydrogen
atoms and cleavage of intra-ring led to higher char yield
(Matsuzawa et al., 2001).
Due to the disadvantage of TG that the yields and characteriza-
tion of oil and gas cannot be established, many researchers have
305
used bench-scale reactors, such as fluidized bed and fixed bed, to
study the co-pyrolysis of PVC with biomass. Consisting with TG
results that biomass postponed PVC pyrolysis, Saeed et al.
(2004a) also found that the mixtures of bottle-grade PVC with
wood degraded at higher temperatures compared with 100% PVC
in fluidized bed. In terms of product distribution, Zevenhoven
et al. (2002) pyrolyzed the mixtures of PVC with wood at 250–
400 °C in quartz tube reactor and found that experimental amount
of combustible carbon compounds in volatiles for PVC/wood mix-
tures was slightly less than predicted one, which was consistent
with more char yields obtained in TG. Çepelioğullar and Pütün
(2014) pyrolyzed mixtures of PVC with hazelnut shell, sunflower
residues and E.rigida in fixed bed at slow heating rate of
10 °C min 1 from room temperature to the final temperature of
500 °C. In this study, increased char yield was also obtained for
mixture of PVC with biomass compared with theoretical yield,
whereas gas yield showed opposite trend and tar did not change
obviously. Moreover, the mixtures had the maximum content of
PAHs and derivatives, which was found mainly in pure PVC decom-
position, indicating PVC affected oil characterization significantly.
However, an increased tar yield has been observed for mixtures
of PVC with three biomass components (hemicellulose, cellulose
and lignin) during fast co-pyrolysis at 800 °C in a fixed bed (Zhou
et al., 2015c). The author proposed that biomass and/or bio-char
acted as a catalyst in promoting the chain scission of PVC produc-
ing more tars. Moreover, decreased amount of PAH was obtained
from mixture of PVC with three biomass components, which
contradicted with other researches (Çepelioğullar and Pütün,
2014; Çepelioʇullar and Pütün, 2014).
Decreased HCl emission has also been observed during co-
pyrolysis of PVC with biomass (Duangchan and Samart, 2008;
Kuramochi et al., 2008; Zhou et al., 2015c). Kuramochi et al.
(2008) studied the co-pyrolysis of PVC with two types of biomass
and three constituents (cellulose, hemicellulose and lignin) in a
fixed bed at 600 °C. It was found that HCl emission was signifi-
cantly reduced by wood. They further pyrolyzed mixtures of PVC
with three constituents separately. The results showed that cellu-
lose had little effect on HCl emission, whereas hemicellulose and
lignin can reduce HCl emission and less than 5% of Cl was released
from PVC/hemicellulose mixture. However, Zhou et al. (2015b)
found that cellulose can also decrease HCl emission similar with
hemicellulose and lignin. Duangchan and Samart (2008) performed
co-pyrolysis of mixture of PVC with cattle manure in fixed bed.
Cattle manure provided a large amount of basic nitrogen com-
pound to react with HCl and reduced HCl emission. This is because
that at temperature higher than 250 °C, nitrogen compound
decomposed to ammonia gas and hydrocarbon compound
(Samart and Duangchan, 2004). It seems that biomass rich in basic
nitrogen compounds is beneficial for controlling HCl emission.
Consisting with most researchers, the presence of cattle manure
also lowered the oil yield by approximate 17% and chlorine content
in oil, whereas char and gas yields increased by 23.5% and 13.9%
separately.
From above analysis, it seems that synergistic effect of co-
pyrolysis of PVC with biomass can be classified as (1) lower the
Table 4
Glass-transition and melting temperatures of plastics (°C) (Kalpakjian, 1997).
Material Glass-transition temperature Melting temperature
PP 14 176
PS 100 239
HDPE 90 137
LDPE 110 115
PVC 87 212
ABS Approximate 175
306 J. Yu et al. / Waste Management 48 (2016) 300–314

Table 5 in TG. They found that negative synergistic effects were observed
Summary of co-pyrolysis of PVC-containing mixtures in TG. in the temperature below about 370 °C, while positive synergistic
Mixtures Interaction effect effects happened at higher temperature. The negative synergistic
PVC/HDPE(1:1)  No obvious effect on dehydrochlorination stage effects might be that the released HCl from PVC was temporarily
(Miranda et al.,  Maximum peak from PVC(II) and HDPE delayed bound in the complex structure of the coal or reacted with calcium
2001a) 14 °C components naturally present in coals forming calcium chloride,
 Increased residue quantity while the positive synergistic effects may be that the reactive rad-
PVC/LDPE(1:1) (Miranda  No effect on dehydrochlorination stage icals that originated from cracking of polymer bonds may react
et al., 2001a)  Maximum peak from PVC(II) and LDPE delayed with fragment radicals produced from cracking of coals so as to
10 °C
 Increased residue quantity
accelerate the stabilization of cracking products of coal. Therefore,
secondary condensation, recombination, and cross-linking reac-
PVC/PE(1:1) (Wu et al.,  No effect on dehydrochlorination stage
2014b)  The pyrolysis of mixtures process occurred later
tions between reactive moieties from the thermal degradation of
20 °C than the predicted one for second stage coal were suppressed. Saeed et al. (2004a) performed co-
 Large amount of unsaturated hydrocarbon groups pyrolysis of PVC with coal in a two-stage test facility. The first stage
appeared while alkynes decreased; ACH3A and was a bubbling fluidized bed where fuel was pyrolyzed in 200–
ACH2A disappeared
400 °C, while the second reactor is a circulating fluidized bed oper-
PVC/PE (Zhou et al., The overlap ratio is 0.987 indicating absence of ated at 800 °C. A strong interaction was also observed: the peak
2015b) interaction
release of HCl was delayed by 19 °C.
PVC/PE (Munther et al.,  Increase in final weight of 7.5%
2010)  Peak from PVC(II) and PE delayed 8 °C
PVC/PE (KnÜMann and  No effect on dehydrochlorination stage 3.3. PVC/other plastics blends
Bockhorn, 1994)  Peak from PVC(II) and PE moved higher
temperature
The interaction between different polymers strongly depends
PVC/PS (Wu et al.,  The actual TGA curve is fitted well with the fitted
on nature of the polymer. As shown in Fig. 5, different categories
2014b) value in the first decomposition process of PVC
until PS begins to decompose obviously of plastics behave differently in terms of onset temperature, weight
 Peak from PVC(II) and PS delayed 10 °C loss rate and char yields. The decomposition of PVC can be divided
PVC/PS (Munther et al., Peaks from PVC (I)/PVC(II) and PS delayed into two stages: dehydrochlorination stage and breakdown of the
2010) intermediate from dehydrochlorination stage, while that of other
PVC/PS(1:1) (Miranda  Peak from PVC (I) and PS slighted delayed plastics is single-stage decomposition process. The different beha-
et al., 2001a)  PVC (II) and PS was slighted stabilized viors of plastics make the decomposition of mixtures more com-
PVC/PS (Dodson and Peaks from PVC (I)/PVC(II) and PS delayed plex. The interaction between different polymers also strongly
McNeill, 1976) depends on miscibility of the polymer or the degree of phase dis-
PVC/PP (Day et al., 1996) The onset temperature of dehydrochlorination was persion. Different for biomass, PE, PS, PPS, PVC and ABS melt prior
retarded and weight loss associated with the to the degradation as shown in Table 4. Therefore, upon heating,
process appears much less than anticipated the homogeneous mixtures can be formed due to melting phe-
PVC/PP (KnÜMann and Peak from PVC(II) and PP delayed nomenon. In a heterogeneous blend, interactions occur in the
Bockhorn, 1994) phase boundaries, whereas in homogeneous samples, the degrada-
PVC/PP (Miranda et al.,  HCl evolution retarded tion products of one polymer are directly in contact with the other
2001a)  Peak from PVC (II) and PP slighted delayed polymers so that their combined effect on the thermal degradation
 Increased residue quantity is stronger. The degradation products of one polymers can stabilize
PVC/PP (Day et al., Peak from PVC(II) and PP delayed or destabilize the other polymers in the blend (Miranda et al.,
1993,, 1994) 2001a).
PVC/ABS (Gawade et al.,  Decomposition rate of actual blends is less than The interaction of PVC with other plastics were extensively
2007) expected studied in TG because reaction rate and decomposition tempera-
 Increased in onset temperature of degradation
with increase in ABS
ture, being good indicators of interaction, can be easily obtained
from TG curves. Studies on the plastics interaction within binary
PVC/ABS (Czégény et al.,  The dehydrochlorination rate was enhanced by
2012) ABS
mixtures in TG are summarized in Table 5. Generally, it can be con-
 Second peak is not much affected by ABS cluded that the dehydrochlorination stage (first peak) of PVC
PVC/ABS (Day et al., The dehydrochlorination reaction was stabilized by
degradation was not obviously affected by PE, whereas the maxi-
1996) ABS mum peak corresponding to decomposition of PE and intermedi-
ates (mainly polyene) from dehydrochlorination stage of PVC,
was delayed to different extent due to interaction. Moreover,
pyrolysis temperature of biomass, (2) increased char yields and (3) increased char yields has been obtained for PVC/PE mixtures indi-
reduced HCl emission. However, the oil yield and PAH amount in cating strong interaction. Different from PE, the dehydrochlorina-
oil was still controversial, which needs more work in future. tion stage and second stage of PVC were all delayed by PS, even
though Wu et al. (2014b) showed the absence of interaction in
the first decomposition process of PVC until PS began to decom-
3.2. PVC/coal blends pose. PP showed greater effect on PVC decomposition. The degra-
dation reaction of polymer included random scission,
A strong interaction was also observed for the co-pyrolysis of depolymerisation, intramolecular transfer reaction, and inter-
coal and PVC in TG (Nabeel et al., 2009; Munther et al., 2010). In molecular transfer reaction which reduced the molecular weight
the temperature interval from approximately 280–360 °C, corre- of the polymers (Beyler and Hirschler, 2002; Wilkie and
sponding to dehydrochlorination of PVC, a significant delay was McKinney, 2004). The interaction of various products from PVC
observed by Munther et al. (2010): dehydrochlorination of PVC and PE/PP/PS may give rise to some cross products formed from
was delayed by 16 °C and was slower and broader than expected. the radicals or molecules which can play an important role in
Meng et al. (2015) also studied the co-pyrolysis of PVC and coal degradation of blends.
 J. Yu et al. / Waste Management 48 (2016) 300–314 307

Table 6
The co-pyrolysis of PVC with PE/PP/PS/ABS in bench-scale reactor.

Authors Mixtures Experiments Yields of Gas (G), Liquid (L), Wax (W) and
Solids (S) (wt.%)
Sakata et al. (1996) PE/PVC (10:0) Fixed bed, Heating rate: 3 °C/min, 430 °C L + W: 69.2; G:8.5; S:22.3
PE/PVC (1:9) L + W: 53.9; G:14.2; S:31.9
PE/PVC (2:8) L + W: 44.9; G:18.5; S:36.6
PE/PVC (0:20) L + W: 4.7; G:63.2; S:32.1
Uddin et al. (1999) PE/PVC Fixed bed, Heating rate: 3 °C/min, 430 °C L + W: 67.9; G:17.5; S:14.6
Cl-L: 2.9; Cl-G:96.6; Cl-S:0.2
Cnp:13.4
PP/PVC Fixed bed, Heating rate: 3 °C/min, 380 °C L + W: 73.2; G:12.8; S:14.0
Cl-L: 12.2; Cl-G:89.4; Cl-S:0.1
Cnp:13.0
PS/PVC Fixed bed, Heating rate: 3 °C/min, 360 °C L + W: 60.4; G:12.3; S:27.3
Cl-L: 6.0; Cl-G:91.8; Cl-S:0.5
Cnp: 9.2
Williams and PS/PVC Fixed bed, Heating rate: 25 °C/min, 700 °C Actual: L + W: 12.7; G:37.8 (HCl: 24.0);
Williams (1999) S:12.7
Predicted: L + W: 8.7; G:29.5 (HCl: 26.5);
S:8.7
Miranda et al. PE/PP/PS/PVC Fixed bed, Heating rate: 10 °C/min, 520 °C Actual: Heavy L:10.56; Light L: 20.53; W:
(2001b) 62.03; G:5.62; S:1.20
Calculated: Heavy L: 9.10; Light L: 20.08;
W: 62.69; G:6.27; S:1.25
Bhaskar et al. PE/PP/PS/PVC Fixed bed, Heating rate: 15 °C/min, 430 °C L + W: 65.4; G:28.7; S:5.9
(2006) PE/PP/PS/PVC Fixed bed, Heating rate: room temperature to 330 °C at 5 °C/min, then L + W: 60.9; G:28.2; S:10.9
holding for 2 h, to 430 °C at 15 °C/min
Miskolczi et al. PVC:PE/PP/PSS: 0%, Horizontal tube bed, 530 °C G: 2.8–3.2%; Gasoline: 18.4–24.8%; Light
(2009) 0.5%, 1%, 2%, 3% L:15.3–32.0%
Day et al. (1999) ABS Tube reactor 700 or 900 °C Mass loss: 700 °C: 54.8; 900 °C: 86.9
PVC Mass loss: 700 °C: 64.5; 900 °C: 71.9
ABS/PVC(1:1) Predicted Mass loss: 700 °C: 59.7; 900 °C:
79.4
Side by side blending: Actual Mass loss:
700 °C: 58.8; 900 °C: 83.3
Intimate blending: Actual Mass loss:
700 °C: 67.5; 900 °C: 80.6
Brebu et al. (2004b) ABS Fixed bed, Heating rate: 10 °C/min to 400 °C then 1 °C/min to 450 °C L + W: 72; G:5; S:24
ABS/PVC(8:2) L + W: 50; G:17; S:38
ABS-Br L + W: 34; G:5; S:61
ABS-Br/PVC(8:2) L + W:41; G:14; S:45
Brebu et al. (2004a) PE/PP/PS + ABS-Br Fixed bed, Heating rate: 5 °C/min, 450 °C L:73; W: 3; G:11; S:13
Cnp:9.7
PE/PP/PS + ABS-Br L:62; W: 14; G:20; S:4
+ PVC Cnp:9.4

Cnp:Average carbon number in liquid.

Apparently, the co-pyrolysis of PP or PS with PVC could delay
the initial degradation of PVC, whereas the interaction of interme-
diates from dehydrochlorination stage of PVC with PP/PE/PS was
responsible for increased char residues. It was proposed that mix-
ture containing PVC and PP/PE/PS presented two types of interac-
tion effect (Miranda et al., 2001a): (1) PP/PS stabilized the HCl
evolution (2) The intermediates from PVC stabilized PP/PE/PS.
Kulesza and German (2003) proposed that the interaction between
of PP/PE/PS and HCl released at the dehydrochlorination stage
decreased the rate of dehydrochlorination process since part of
HCl was reacted, therefore, the extent of autocatalysis was
depressed. Miranda et al. (2001a) also suggested that an inter-
molecular transfer from Cl
radicals to both the PVC and other plas-
tics was responsible for the retarded dehydrochlorination stage
due to less available Cl
radicals to initiate the dehydrochlorination.
Comparatively, the increased char yield was mainly caused by the
interaction between the intermediates from PVC dehydrochlorina-
tion with radical intermediates from PP/PE/PS by intermolecular
chain transfer mechanism. A greater effect of PP on the stabiliza-
tion of HCl production was been observed which could be that
the PP degradation was attributed to the random scission plus
extensive intermolecular transfer involving tertiary H-abstraction
from the polymer by the primary radical, where H-abstraction
from PP by Cl
radicals can be easier than H-abstraction from PVC.
PVC/ABS blends are used in a great variety of application, such
as interior truck panels, communication relays, electrical housing,
mass transit interiors, etc. Therefore, the co-pyrolysis of PVC/ABS
was also studied by researchers. Day et al. (1996) found that the
weight loss of ABS/PVC mixture associated with the dehydrochlo-
rination stage of PVC was much less than expected and proposed
that ABS was bestowing a certain amount of stability to the initial
dehydrochlorination of PVC. Gawade et al. (2007) prepared ABS/
PVC blends via melting blending method. The TG results showed
that a slight increase in the onset temperature of degradation
was observed with increase in percentage of ABS in mixtures indi-
cating higher heat stability. Moreover, the mass loss of actual
blends was less than that expected one. Therefore, incorporation
of ABS affected the decomposition pattern, rate and overall chem-
istry. However, Czégény et al. (2012) proposed the dehydrochlori-
nation rate of PVC was enhanced by the presence of ABS.
Due to the interaction, different mixtures behaved differently in
terms of the product distribution, oil characterization and gas
308 J. Yu et al. / Waste Management 48 (2016) 300–314

Table 7
Chloroorganic compounds in liquid from pyrolysis of PVC containing plastics.

Authors Sample Chloroorganic compounds

Huggett and Levin PVC Chlorobenzene
(1987) Chloroethane
Chloropropene
Dichloroethylene
Dichlorobutadiene
Scheme 1. Plausible steps for the formation of chlorinated hydrocarbons during Dichloropemene
pyrolysis of PVC mixed plastics (Bhaskar et al., 2006). Trichloropropane
Dichlorobenzene
Trichlorobenzene
p-Chlorobenzonitrile
composition. In order to get deep insight into the mechanism of
Dichlorobenzonitrile
interaction, the co-pyrolysis of PVC with other plastics have been
Miranda et al. PVC 3-Chloro-2-methyl-1-butene
studied in bench-scale reactor. The product distribution of PVC
(2001b) 1-Chlorocyclopentene
containing mixtures are summarized in Table 6. Authors may reach 1-Chloro-3-methyl-1-butane
different conclusion on interaction between PVC with other plas- Chlorobenzene
tics in terms of product distribution and oil characterization, etc. 3-Chlorocyclohexene
Therefore, several works on interaction of PVC with other plastics 1-Chloro-2-ethylbenzene
3-Chloro-3-methyl-heptane
are summarized below.
Benzylchloride
Williams and Williams (1997) compared the theoretical and 2-Chloro-ethylbenzene
experimental product distribution from the pyrolysis of HDPE/ Ethylchloromethylbenzene
LDPE/PP/PS/PET/PVC mixtures. The HCl from mixtures was only (3-Chloro-1-propenyl)benzene
3-Chloroallylbenzene
one third of that expected according to its PVC content due to
3-Chloro-1-phenyl-2-butene
the occurrence of organochlorine compounds in liquid oil. The FTIR 2-Chloro-2-butenyl)benzene
analysis of oil from plastic mixture indicated the amount of aro-
Grimes et al. PVC Chlorobenzene
matic and oxygenated groups were much higher than expected (2006) p-Dichlorobenzene
by simple accumulation of the oil fraction derived from each poly- o-Dichlorobenzene
mer, indicating chlorine was partially transferred to liquid oil dur- 1,2,4-Trichlorobenzene
ing co-pyrolysis. Another work by Williams and Williams (1999) 1,2,4,5-Tetrachlorobenzene
Pentachlorobenzene
studied the co-pyrolysis of PVC with PS. A clear interaction has
Hexachlorobenzene
been observed for PVC/PS mixture with much higher amount of 2,3,7,8-Tetrachloro-dibenzo-p-dioxin
gas than expected at the expense of liquid oil. The oil from the
Miranda et al. HDPE/LDPE/ 2-Chloro-2-methylpentane
pyrolysis of the PVC/PS mixtures gave a wholly aromatic oil. The (2001b) PP/PS/PVC 3-Chloro-3-methylpentane
benzene concentrations for PVC pyrolysis alone was 30.7%; with (2-Chloro-ethyl)benzene
PS present this was markedly reduced to 1.7%. The molecular Brebu et al. PVC/ABS-Br Hydrochloric acid
weight distribution and number and weight averaged molecular (2004b) 1-Chlorobutane
weights of the oil produced from the mixed plastics pyrolysis were 1-Chloroethylbenzene
2-Chloro-1,4-dimethylbenzene
also markedly reduced compared to those of the individual plastic
3-Chloropropanenitrile
pyrolysis oil/wax. Differently, Blazsó et al. (1995) investigated the 2-Chlorophenol
co-pyrolysis of PVC/PE and found that the yields of aliphatic, aro-
Kulesza and PVC/PET Methane, bis(2-chloroethoxy)
matic and polyaromatic products were strongly reduced by the German (2003) 4-Chlorobenzoic acid, ethyl ester
presence of PVC. The authors proposed that HCl from PVC pro- 3-Chlorobenzoic acid, ethyl ester
moted initial PE chain scission at the weakest points but hindered Benzoic acid, 2-chloroethyl ester
b-scission of the macroradicals. Sakata et al. (1996) also pyrolyzed 4-Methylbenzoic acid, 2-chloroethyl
ester
mixtures of PVC with PE in fixed bed at slow heating rate. It was
4-Chlorobenzoic acid, 2-chloroethyl
found that the addition of PVC to PE decreased the overall liquid ester
products yield and promoted the degradation of PE into low- 4-Formylbenzoic acid, 2-chloroethyl
molecular-weight liquid hydrocarbons. The authors suggested that ester
1,4-Benzenedicarboxylic acid, 2-
the interaction between PE and free radicals produced from the
chloroethyl, methyl ester
decomposition of PVC might promote the degradation of PE. In a 1,4-Benzenedicarboxylic acid, 2-
parallel study (Uddin et al., 1999), the co-pyrolysis of PE/PVC at chloroethyl, ethyl ester
420 °C, PP/PVC at 380 °C and PS/PVC at 360 °C were carried out 1,4-Benzenedicarboxylic acid, mono-
in fixed bed reactor. For three mixtures, PP/PVC produced highest 2-chloroethyl ester
1,4-Benzenedicarboxylic acid, di-2-
amount of liquid yield being 73%, while lowest of 61% for
chloroethyl ester
PS/PVC. For chlorine balance, 88–96 wt% of chlorine in sample
was evolved as gaseous HCl, 3–12 wt% in liquid phase, and less Bold: main compounds in oil.
than 2 wt% remained as residue. For all mixtures, more than 89%
of Cl were distributed into gas as HCl, with the rest mainly in liquid
oil. The amount of chloroorganic compounds in oil from PP/PVC, degradation of PVC and those of the other polymers (Shiraga et al.,
PS/PVC and PE/PVC were 12,700, 7400 and 2800 ppm, respectively. 1999). The formation of chlorinated hydrocarbons might be due to
It led to the suggestion that, if only organic chlorine compounds the following reactions: Cl radicals or free HCl from PVC reacting
had been formed by the degradation of PVC, all the chlorine con- with cracked hydrocarbon species. Shiraga et al. (1999) proposed
tent in the oil would have been the same. However, the amount that the chlorine-containing compounds were formed by the reac-
of chloroorganic compounds in liquid products varied according tion of HCl with products, such as the branched olefins, from the
to the type of degraded plastics; thus it was suggested that organic degradation of PP/PS/PE, which was proved by Bhaskar et al.
compounds are formed by a reaction between the products of the (2006). The author performed co-pyrolysis of PE/PP/PS/PVC with
 J. Yu et al. / Waste Management 48 (2016) 300–314
a two-step temperature program (step I: room temperature to
330 °C; kept at 330 °C for 2 h; step II: 330 °C to final temperature
430 °C) and single-step rate of heating (room temperature to
430 °C at 15 °C/min). The two-step pyrolysis of PE/PP/PS/PVC pro-
duced chlorine free liquid hydrocarbons, whereas the chlorine in
liquid phase from single-step pyrolysis of PE/PP/PS/PVC was
390 ppm. For the single-step pyrolysis, HCl from decomposition
of PVC reacted with olefinic hydrocarbons produced from PP/PS/
PE forming chlorinated hydrocarbons as shown in Scheme 1.
However, for the two-step pyrolysis, the evolved HCl was carried
out from the reactor below 330 °C before the reaction with
PP/PS/PE, thus the formation of chlorinated hydrocarbons can be
avoided. Thermal degradation of PE/PP/PS leaded to the formation
of conjugated double bonds while the HCl released from PVC
attacked these double bonds resulting in the formation of toxic
chlororganic compounds.
Miskolczi et al. (2009) pyrolyzed the plastic mixtures (HDPE, PP,
PS and PVC) in tube reactor at 530 °C. The mixtures could be con-
verted into gases, gasoline and light oil with yields of 36.9–59.6%,
which was significantly increased with an increasing percentage of
PVC in mixtures. The yields of valuable volatile products (gasoline
and light oil) and aromatics (from 30.53% to 35.42%) increased with
an increasing PVC percentage in mixtures. Moreover, the chlorine
content in oil also increased considerably with the PVC content,
even though most chlorine were found in gases (0.66–3.45%). The
chlorine concentration was in the range of 46–2129 ppm in gaso-
line and 132–2201 ppm in light oil.
Brebu et al. (2004b) studied the co-pyrolysis of PVC/ABS and
PVC/ABS-Br in tube furnace at 450 °C. For PVC/ABS mixture, the
oil yield was even lower than only considering the decomposition
of ABS copolymer, indicating strong interaction between ABS and
PVC, which leaded to the formation of heavy compounds in the
residue. Conversely, for PVC/ABS-Br, the oil yield was increased
and also the oil accumulation rate. The difference in thermal degra-
dation of ABS/PVC and ABS-Br/PVC was further evidenced by the
distribution of N, Cl, Br and O in oil. The total amount of chlorine
in oil was of 3640 ppm for ABS-containing mixture and of
2670 ppm for ABS-Br-containing mixture. Thermal degradation of
ABS-Br/PVC mixture led to higher amount of 8420 ppm Br (com-
pared to 2630 ppm in ABS-Br oil) and lower amount of
11,320 ppm O (14,330 ppm for ABS-Br) indicating interaction
between ABS-Br and PVC. The presence of PVC in ABS also reduced
the yield of N in oil. The presence of compounds containing both Cl
and N in pyrolysis oil also proved the existence of interaction
between PVC and ABS-Br. In a parallel study (Brebu et al., 2004a),
PE/PP/PS/ABS-Br/PVC and PE/PP/PS/ABS-Br/PET/PVC mixtures were
pyrolyzed in tube furnace at 450 °C separately. The formation of
liquid products in the absence of PVC was about 3 min earlier than
that in the presence of PVC. It was supposed that the effect of PVC
on pyrolysis of ABS-Br containing polymer mixture was manifested
especially during the formation of light compounds by primary
degradation process. Similarly, PVC increased the N and Br in oil
and the effect can be accelerated by PET. Day et al. (1999) also
found that the presence of PVC in ABS reduced the yield of nitrile
products.
As discussed above, part of chlorine were transformed to liquid
product from pyrolysis of PVC containing plastics. Therefore, the
main chlorinated hydrocarbons formed during the pyrolysis of
PVC containing plastics are summarized and given in Table 7. It
can be observed that chlorobenzene is the main chlorinated hydro-
carbon from PVC pyrolysis, even though the chlorinated hydrocar-
bons obtained from different experiment varied significantly.
Miranda et al. (2001b) compared the chlorinated hydrocarbons
from PVC and HDPE/LDPE/PP/PS/PVC respectively. It was found
that 2-Chloro-2-methylpentane and (2-Chloro-ethyl)benzene were
only found in oil from HDPE/LDPE/PP/PS/PVC mixture, indicating
309
the interaction of different components in the mixture during
pyrolysis. New chlorinated hydrocarbons were also found for
PVC/ABS-Br and PVC/PET mixtures. As discussed in Scheme 1, the
HCl from PVC can react with pyrolysis-derived unsaturated com-
pounds from degradation of PE/PP/PS forming different chlorinated
hydrocarbons.
4. Catalytic dechlorination
Even though pyrolysis are accepted as promising means of PVC
recycling, one potential problem in the thermal degradation of PVC
is the generation of oil containing significant amount of Cl. The use
of Cl-containing oil will cause severe unit corrosion and the release
of environmental toxins. Therefore, necessary measures should be
taken in terms of conversion of PVC into high quality oil. Compared
with conventional pyrolysis, catalytic cracking can inhibit the for-
mation of chlorinated hydrocarbons, lowering the reaction temper-
ature, shortening residence times and enhancing the selectivity of
products (Aguado et al., 2006). Catalytic dechlorination involves
the selective cleavage of one or more CACl bonds, lowering toxicity
and generating reusable raw materials.
Sakata et al. (2003) clarified the two different catalytic dehalo-
genation processes using various carbon composites of iron oxides
and calcium carbonate as the catalyst/sorbent. The first one was a
two-step process: degradation of mixed halogenated waste plastics
(first step) and catalytic dehalogenation of organic chlorine com-
pounds from mixed plastic-derived oil (second step). The second
one (a single-step process) was the simultaneous degradation
and dehalogenation of PVC-containing plastics into Cl-free liquid
products. For the two-stage process, oil from the first stage pyrol-
ysis contained 0.2% chlorine. In the second stage, a high dechlori-
nation activity was observed for various iron-based catalysts. The
single-step degradation and catalytic process was carried out using
a CaAC catalyst. The liquid products obtained contain 360 ppm
chlorine without catalyst. However, the amount of chlorine was
zero (undetected) using a CaAC sorbent, indicating that the chlo-
rine compounds were completely removed from the liquid prod-
ucts. The catalytic dechlorination depended on both catalysts and
processes. Similarly, Lopez-Urionabarrenechea et al. (2012) stud-
ied pyrolysis of PVC-containing plastics by four different methods:
(1) Conventional thermal pyrolysis (2) Conventional catalytic
pyrolysis; (3) Catalytic stepwise pyrolysis; (4) Non catalytic
Fig. 6. The normalised amount of HCl from the pyrolysis of PVC–MO mixture at
800 °C, plotted as a function of optical basicity of the corresponding oxide. (Masuda
et al., 2006).
310 J. Yu et al. / Waste Management 48 (2016) 300–314
dechlorination step + catalytic pyrolysis. The catalyst used was
ZSM-5. The gas yield followed the sequence of non-catalytic
dechlorination step + catalytic pyrolysis  conventional catalytic
pyrolysis > catalytic stepwise pyrolysis > conventional thermal
pyrolysis. The reason may be that zeolite lost some activity during
the dechlorination step due to the melting phenomenon of plastic
during dechlorination step, which may physically block the cata-
lyst pores. For catalytic stepwise pyrolysis, the yield of heavy
hydrocarbons increased up to 9.5%, which was in agreement with
the activity loss of catalyst. For Non-catalytic dechlorination step
+ catalytic pyrolysis, the Cl in oil was lowest. The optimum proce-
dure in terms of quality and chlorine amount of the products was
the combination of first a low temperature step without catalyst,
and second the catalytic pyrolysis step.
Therefore, the catalytic dechlorination of PVC can be divided
into three methods: (1) Combining thermal degradation with cat-
alytic dechlorination of PVC to obtain high quality of Cl-free oil;
(2) Catalytic hydrodechlorination of oil from pyrolysis of PVC-
containing plastic to generate Cl-free oil; (3) Non-catalytic dechlo-
rination step at low temperature followed by catalytic pyrolysis at
high temperature.
4.1. Simultaneous catalytic degradation and dechlorination
Most catalytic dechlorination studies of PVC up to now mainly
focused on using the catalysts as adsorbents for the evolved HCl
or as inhibitors of HCl formation. Masuda et al. (2006) compared
catalytic pyrolysis of PVC using eight metal oxides at 400 and
800 °C. The emission of HCl depended significantly on the oxides
used, which was strongly concerned with the chlorine fixing ability
of oxides. The emission of HCl decreased with increasing basicity of
metal oxide as shown in Fig. 6. However, large deviation was found
for the trivalent rare earth oxide systems. Ln2O3 showed greatest
ability to fix considerable amount of chlorine in the form of LnOCl.
Chlorobenzene compounds, one of the precursors of PCDD/Fs, were
decreased by most metal oxides except for Fe2O3 and CeO2, and
Ln2O3 and ZnO showed greatest suppression of chlorobenzene
formation.
Yanik et al. (2001) compared the catalytic effect of Red mud
(mainly Fe2O3, Al2O3 and SiO2), c-Fe2O3 and SiO2
Al2O3. The use
of red mud in vapour-phase-contact mode led to more HCl fixation,
but also increased the chlorine amount in oil due of the reaction
between fixed HCl and adsorbed degradation products on Red
Mud, indicating the formation of some organic chlorine com-
pounds may be promoted by the interaction of HCl and catalysts.
Brebu et al. (2005) performed catalytic pyrolysis of PE/PP/PS/
ABS-Br/PVC mixtures at 450 °C using FeOOH, FeAC composite,
CaCO3 and CaAC composite. Iron catalysts were found to be effec-
tive in removing more than 90% of organic Br from oil, while cal-
cium catalysts had higher efficiency for chlorine removal, which
is consistent with Masuda et al. (2006). Zhou et al. (2004) synthe-
sized an AlAMg catalyst for catalytic pyrolysis of PP/PVC, LDEP/
PVC, PS/PVC and LDPE/PS/PP/PVC mixtures. For all mixtures,
AlAMg decreased Cl content in oil significantly: the chlorine in
oil from PP/PVC pyrolysis was significantly decreased from 16500
to 4400 ppm. The AlAMg composite oxide shared both acidic and
basic properties. The basic characters were similar to those of
MgO, and some acidic properties was from Al2O3, which explained
the double effects of both cracking and dechlorination ability of the
AlAMg. Uddin et al. (2002) investigated the thermal and catalytic
degradation of HIPS-Br/PVC using carbon composite of iron oxide
catalyst at 430 °C. Thermal degradation of HIPS-Br/PVC yielded liq-
uid products with 55,000 ppm bromine and 4300 ppm chlorine,
whereas catalytic degradation waste produced halogen-free clean
oil. The average carbon number of the liquid products produced
during catalytic degradation (9.3) of waste plastics was less than
that of the thermal degradation (10.4)
Apart from metal oxides and silica-alumina, zeolites, FCC cata-
lysts and mesostructured catalysts have been utilized for the cat-
alytic pyrolysis of plastics to remove Cl and upgrade oil. Lin et al.
(2010, 2011) performed catalytic pyrolysis of PE/PP/PS/PVC mix-
tures in fluidized bed reactor using zeolitic catalysts (ZSM-5,
HUSY), non-zeolitic catalysts (Silicalite) and zeolite-based modi-
fied FCC catalyst (SAHA, Rcat-s1). Zeolitic catalysts produced much
more C1-C4 hydrocarbon gases than other catalysts. The maximum
reaction rate was observed after 2 min for zeolitic catalysts and
3 min for other catalysts, which then decreased significantly. The
results revealed that the catalytic controlling parameters will be
not only the total number of acid sites but also the number of
accessible acidic sites. Keane et al. (2007, 2009) performed cat-
alytic pyrolysis of PVC in a continuously stirred tank reactor at
450 °C. The catalyst used was Pd/Al2O3. It was found that the pres-
ence of the catalyst resulted in a decrease in the liquid-phase Cl
content (by a factor of up to 560), and an increase in the gas phase
C1AC4 hydrocarbon content with a higher overall alkane content
(ethane/ethylene in excess of 20). Wu et al. (2014a) processed
HDPE/PVC by catalytic pyrolysis-reforming for hydrogen and
high-value carbon nantubes using NiAMnAAl catalyst. Lower
hydrogen production was observed for the HDPE/PVC compared
with HDPE in the non-catalytic experiment. When NiAMnAAl cat-
alyst was added, the difference of hydrogen production between
those two plastic samples was reduced. At the same, the presence
of chlorine in HDPE/PVC waste plastic mixture can poison the cat-
alyst during the formation of carbon nantube due to the adsorption
of HCl (Lingaiah et al., 2001a). Moreover, the adsorbed HCl can
react with polymer derived products generating chlorinated com-
pounds, which could increase chlorine amount in liquid (Lopez-
Urionabarrenechea et al., 2012).
4.2. Catalytic dechlorination of oil
The catalytic dechlorination of Cl-containing oil was mainly
performed using various metal oxides. Lingaiah et al. (2001b)
upgraded the PE/PP/PS/PVC derived oil in continuous stirred tank
reactor at 410 °C using the FeCl2/SiO2 catalyst. The various
chloro-organic compounds in oil (ca. 1600 ppm) were mainly
2-chloro-2-methylpropane, 2-chloro-2-methylpentane, chloro
ethylbenzene and 2-chloro-2-phenylpropane. During the catalytic
dehydrochlorination, the chloro-organic compounds in oil can be
effectively removed, whereas the carbon number distribution of
the fuel oil did not change considerably. In a parallel study
(Lingaiah et al., 2001a), catalytic dechlorination of PVC-
containing mixed plastic-derived oil was performed using iron
oxide and iron oxide–carbon composite catalysts. The catalyst
showed an initial high removal of chlorine and the dechlorination
activity was stabilised after initial deactivation due to the adsorp-
tion of HCl. However, the catalyst deactivation was suppressed by
using hydrogen and helium due to the removal of HCl from catalyst
surface. It was believed that iron oxide would be able to weaken
the CACl bond in the chloroorganic compounds. The author pro-
posed that the iron oxide initially acted as catalyst and then it con-
verted to iron chloride phase by reacting with the produced HCl;
the iron chloride phase was also active for the dechlorination of
chloroorganic compounds, which was consistent with their previ-
ous work (Lingaiah et al., 2001b). Even though the removal of chlo-
rine was high, none of the catalysts studied in this reaction greatly
affected the carbon number distribution during the dechlorination.
Considering high amount of iron oxide in Red Mud, Lopez-
Urionabarrenechea et al. (2015) carried out the upgrading of chlo-
rinated oils from the pyrolysis of PVC-containing plastics using Red
Mud (mainly Fe2O3, Al2O3 and TiO2) in a stirred autoclave and a
 J. Yu et al. / Waste Management 48 (2016) 300–314
condensation system at 325 °C. Red Mud proved to be a good cat-
alyst, which gave rise to higher quantity of gases and light liquid
fractions and reduced the chlorine amount in the liquid light frac-
tions to the half (<0.1 wt.%) compared to that obtained in thermal
cracking. The chlorine in solid residues increased significantly due
to the fixation of chlorine by Red Mud. Further, the catalytic dehy-
drodechlorination of Cl-containing oil using iron oxide, iron oxide–
carbon composite, ZnO, MgO and Red Mud were compared by
Lingaiah et al. (2001c). The iron oxide were more effective in
removing the chloroorganic compounds. Iron oxide and its carbon
composite were found to be stable in the dehydrochlorination of
municipal waste plastic derived oil, whereas MgO and ZnO cata-
lysts were deactivated during the reaction by HCl.
4.3. Separate dechlorination and catalytic degradation
Lopez-Urionabarrenechea et al. (2012) applied firstly the
dechlorination process of PVC (without catalyst) at low tempera-
ture and then carried out catalytic degradation at higher tempera-
ture. Compared with dechlorination process in the presence of a
catalyst, non-catalytic dechlorination step + catalytic degradation
process produced less styrene and more other compounds, which
may be due to the fact that the catalyst lost its activity during
dechlorination step. In terms of distribution of chlorine in pyrolysis
products, conventional catalytic pyrolysis process produced 1.2 wt
% chlorine, which was higher than of the conventional thermal run
(0.2 wt%) and non-catalytic dechlorination step + catalytic degra-
dation process (0.3 wt%). During dechlorination process, part of
HCl may be retained by catalyst, then the polymer derived prod-
ucts can react with HCl generating chlorinated compounds. For this
reason, the dechlorination step is an essential stage in catalytic
pyrolysis PVC containing plastic waste. Therefore, the optimum
configuration for recycling PVC containing plastic waste by pyrol-
ysis is a staged process consisting of a low temperature (approxi-
mate 300 °C) dechlorination step and then a high temperature
catalytic step. The addition of catalyst should be done after the
dechlorination step, since otherwise the catalyst is deactivated
during such step.
5. Hydrothermal treatment in supercritical or subcritical water
The subcritical water (CW) or supercritical water (SCW) system
have been extensively in upgrading and desulfurization of heavy
oils with or without catalysts (Ates et al., 2014; Timko et al.,
2015). CW/SCW has the advantage of presenting simple and fast
reaction rates and of being a homogeneous reaction without the
Scheme 2. Reaction pathway of PVC decomposition in the presence or absence of supercritical water.
311
limitations of mass transfer. The small hydrocarbons molecules
formed during polymer pyrolysis can easily disperse in liquid
phase, therefore, the chance of subsequent condensation and coke
formation is reduced (Bermejo and Cocero, 2006). In order to get
Cl-free and lighter oil, many researchers have performed pyrolysis
of PVC using CW/SCW.
Xiu et al. (2014) treated waste printed circuit boards and PVC
simultaneously by subcritical water oxidation. It was found that
the dechlorination of PVC, removal of brominated flame retardants,
and recovery of Cu and Pb could be achieved simultaneously by
one step subcritical water oxidation reaction. No noticeable
dechlorination of PVC was observed below 200 °C, whereas dechlo-
rination of PVC increased significantly to 93% at 250 °C, which
reached approximately 100% above 300 °C. Moreover, the Cl in
PVC was nearly completely transferred to aqueous phase.
Kubátová et al. (2002) also studied dechlorination of PVC using
subcritical water. The PVC showed mass loss only above 250 °C.
At both 300 and 370 °C, approximate 44% of the initial PVC
remained as residue. The approximate 56% weight loss at 300
and 370 °C corresponded perfectly with the weight loss expected
if all chlorine were removed from the PVC. GC/MS detected no
organochlorine molecules in oil. Moreover, elemental analysis of
PVC residues showed 1:1 carbon/hydrogen molar ratio, as would
be expected if the PVC residue was composed of high molecular
weight conjugated alkenes (ACH@CHACH@CHA)n, which would
be formed from dehydrohalogenation.
Yoshiyuki et al. (1998) applied supercritical water to investigate
its potential for PVC decomposition. The results showed that
supercritical water treatment was able to break PVC into various
organic compounds in liquid and gas phases. Chlorine atoms in
PVC were recovered as HCl in water and did not contribute to syn-
thesis of organochlorine compounds. One mechanism of sequential
occurrence of three reactions was then proposed: (1) removal of
HCl from PVC by the zipper dehydrochlorination mechanism which
made conjugate double bonds in the polymer chain, (2) breaking of
the polymer chain, and (3) synthesis of aromatic compounds from
the broken chains. Takeshita et al. (2004) treated waste PVC by
hydrothermal decomposition in subcritical and supercritical
regions and also divided the decomposition temperature into three
regions: T < 250 °C, 250 °C < T < 350 °C and 350 °C < T. They pro-
posed that in the first region, PVC went through dehydrochlorina-
tion to form polyene; in the second region, polyene decomposed to
low-molecular weight compounds like carbon dioxide and ben-
zene in the gas phase and acetone, benzene, and benzoic acid,
etc. in the liquid; in the third region, polyene further decomposed
into a large amount of low-molecular weight compounds.
312 J. Yu et al. / Waste Management 48 (2016) 300–314
Chlorinated organic compounds were not observed in the oil from
PVC using subcritical and supercritical water. Nagai et al. (2007)
performed degradation of PVC in supercritical water and proposed
one PVC dechlorination mechanism in the presence or absence of
water as shown in Scheme 2. In the absence of supercritical water,
PVC degradation proceeded through 1 then 3 via ionic chain reac-
tion and through cracking generating aromatic and low molecular
weight compound 4. Under supercritical water condition, OH
nucleophilic substitution occurred competitively with ionic pair
dechlorination to form polyol structures 2. The OH nucleophilic
substitution reaction was accelerated with increasing water den-
sity. However, at temperatures in which water density was higher
than critical point, increasing temperature leads to a lower rate of
polyol 2 formation which can be attributed to (1) increased reac-
tivity of polyene structures formed, (2) dehydration of polyol struc-
tures 2 to yield polyene structures 3, and (3) probable
decomposition and hydrolysis of polyol structures 2 to lower
molecular weight compounds 4.
6. Conclusions
In order to find an environmentally friendly way for treating
PVC, different chemical recycling methods were summarized in
this paper to understand their advantages and disadvantages.
The following conclusions regarding co-pyrolysis, catalytic dechlo-
rination and hydrothermal treatment in subcritical and supercriti-
cal water can be obtained:
(1) PVC degradation is characteristic of two distinct stages: (1)
Dehydrochlorination of the polymer forming de-HCl PVC
and volatiles at low temperature, cracking and decomposi-
tion of the de-HCl PVC at higher temperature. The two stage
of PVC decomposition can be the basis of dehydrochlorina-
tion treatment of PVC. The additives, such as metal oxide
stabilizers and LDH stabilizers, made commercial PVC degra-
dation complicated. The Cl can be adsorbed by LDH and
metal oxide to avoid autocatalytic dehydrochlorination of
PVC.
(2) For co-pyrolysis of PVC with biomass, the dehydrochlorina-
tion of PVC can accelerate the biomass pyrolysis at low tem-
perature range. It is mainly that HCl evolution from PVC may
possibly function as acid-catalyst for the dehydration and
decomposition of the cellulose. The observed increased char
yields for co-pyrolysis of PVC with biomass may be caused
by cellulose. Moreover, HCl emission was reduced by
biomass.
(3) For co-pyrolysis of PVC with other plastics, PP or PS with PVC
could lead to the stabilization of the initial degradation of
PVC, whereas the interaction of intermediates from dehy-
drochlorination stage of PVC with PP/PE/PS increased char
residues.
(4) For simultaneous catalytic degradation and dechlorination,
most metal oxide catalysts were used as adsorbents for the
evolved HCl or as inhibitors of HCl formation. The chlorine
fixing capacity depended on basicity of oxide, while the cat-
alytic effect relied on the acid function of oxide. Zeolites and
noble metal catalysts were found to produce lighter oil,
depending the total number of acid sites and the number
of accessible acidic sites.
(5) In subcritical water, nearly all Cl can be removed at temper-
ature higher than 300 °C. In supercritical water, chlorine
atoms in PVC were recovered as HCl in water and did not
contribute to synthesis of organochlorine compounds. It
was proposed that the decomposition of PVC can be divided
into three stages according to temperature. In the first
region (T < 250 °C), PVC went through dehydrochlorination
to form polyene; in the second region (250 °C < T < 350 °C),
polyene decomposed to low-molecular weight compounds;
in the third region (350 °C < T), polyene further decomposed
into a large amount of low-molecular weight compounds.
Acknowledgement
This research was supported by the National Natural Science
Foundation of China (No. 51576073, No. 51376073) and China
Postdoctoral Science Foundation (2015M572139).
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