Journal of the Japan Petroleum Institute, 59, (6), 243-253 (2016) 243

[Review Paper]

Feedstock Recycling via Waste Plastic Pyrolysis

Shogo KUMAGAI and Toshiaki YOSHIOKA

Graduate School of Environmental Studies, Tohoku University, 6-6-07 Aoba, Aramaki-aza, Aoba-ku, Sendai 980-8579, JAPAN

(Received March 28, 2016)

Recycling of waste plastics is essential for reducing environmental degradation and ensuring future resource
security. The quantity of domestic plastic waste recycled is increasing yearly, reaching 83 % in 2014. However,
only 26 % and 4 % of the recycled waste plastic is treated by mechanical and feedstock recycling, respectively,
whereas 70 % is treated by energy recovery (incineration). Therefore, the mechanical and feedstock recycling
rates must be improved. This review examines the pyrolysis of waste plastics, which is a treatment method
classed as feedstock recycling. Pyrolysis can convert waste plastics, which cannot be treated by mechanical
recycling, into oils and gases. However, polyvinylchloride (PVC) and poly(ethylene terephthalate) (PET) produce
corrosive gases and sublimating substances during pyrolysis, resulting in reduced quality of pyrolysis products,
and damage to the treatment plant. Dehydrochlorination and dechlorination of PVC, in addition to catalytic
pyrolysis of PET using Ca-based catalysts, have been developed. Recent studies into the pyrolysis of major plastics
such as polyethylene (PE), polypropylene (PP), and polystyrene (PS) are summarized here, together with research
on the dry and wet treatment of PVC and the catalytic pyrolysis of PET.

Keywords
Pyrolysis, Waste plastic, Feedstock recycling, Liquefaction, Gasification

1. Introduction recycling. According to the Basic Law for Establishing

the Recycling-based Society, the order of priority of
Plastics are essential materials for various products these techniques is as follows: mechanical recycling
such as packaging and containers, electrical and elec- feedstock recycling ener gy recovery. Therefore,
tronic equipment, and automobiles. Japanese produc- the ideal and actual situations show a wide gap.
tion of polymers was reported as 10.6 million t in 20141), Feedstock recycling is a growing field in Japan, but is
with the majority prepared from finite fossil resources. challenging due to the mismatch with current domestic
Currently, in excess of 150 and 200 different types of recycling systems. However, advances in research and
polymers and additives, respectively, are produced and technical development show the potential to achieve an
distributed within Japan2). Metals and fillers are fur- advanced recycling-based society. In Japan, mono-
ther mixed with these products to achieve the desired merization, blast furnace reduction, coke oven chemical
properties, giving innumerable combinations. Thus, feedstock recycling, liquefaction, and gasification are
no single recycling technique can treat all types of categorized as feedstock recycling. In this paper, we
waste plastics. Consequently, waste plastics are com- focus on liquefaction and gasification, which are based
monly treated by mechanical recycling, feedstock recy- on the pyrolysis technique.
cling, and energy recovery, depending on the waste Pyrolysis converts polymeric materials into gases,
composition and the purpose of the recycled products. liquids, and solids at high temperatures in the absence
The Plastic Waste Management Institute reported that of oxygen. This process cleaves various chemical
9.3 million t of waste plastics were collected in 2014 in bonds in polymers and additives by the action of only
Japan1). The utilized rate (mechanical recycling heat, which is advantageous for low-purity waste
feedstock recyclinge nergy recovery) for collected that cannot be treated by mechanical recycling.
waste plastics was 83 %, and is increasing yearly. Polyethylene (PE), polypropylene (PP), and polystyrene
Utilization can be broken down into 70 % energy recov- (PS) are the main polymeric materials produced world-
ery, 26 % mechanical recycling, and 4 % feedstock wide, so have been widely studied. In addition, these
materials are good quality carbon and hydrogen re-
DOI: [Link]/10.1627/jpi.59.243
sources (PE and PP: 86 % C and 14 % H; PS: 92 % C
To whom correspondence should be addressed. and 8 % H). In contrast, the pyrolysis of polyvinyl
E-mail: yoshioka@[Link] chloride (PVC) and poly(ethylene terephthalate) (PET)

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35.0 wt% gases, 48.4 wt% oil, 14.3 wt% distillation

residue, and 2.2 wt% char. The produced oil con-
tained important aromatic compounds such as benzene,
toluene, xylene (BTX), and styrene in a total yield of
31.4 wt%. In addition, the produced gases had a high
calorific value of 50 MJ/kg. PE- and PP-rich mixed
plastics were pyrolyzed into olefins, such as 21-29 wt%
ethylene, 16-21 wt% propylene, and 5.6-6.6 wt% buta-
diene in a steam atmosphere8). This product composi-
tion is similar to that obtained from the steam cracking
of naphtha. The catalytic pyrolysis of polyolefins
using FCC9) and Ziegler-Natta catalysts10),11) reduced
the operating temperature and increased the quantity of
light hydrocarbons. The effectiveness of the Hamburg
process for various polymeric materials is summarized
Fig. 1 Fluidized Bed Pyrolysis System6) elsewhere12)16) .
Pyrolysis of polyolefins was investigated using a con-
ical spouted bed reactor (CSBR)17)26 ). The following
resins tends to suffer problems with corrosion, clogging advantages were obtained: good heat and material trans-
of the treatment facilities, and production of undesir- fer, low operating pressure, wide particle size and den-
able chlorinated organic compounds. This paper sum- sity without segregation, and absence of defluidization
marizes recent developments in the pyrolysis of major through vigorous contact in the spout and fountain. A
plastics such as PE, PP, and PS, and discusses the 69 wt% gasoline fraction (C5-C10) was recovered from
pyrolysis of PVC and PET. high density polyethylene (HDPE) without defluidiza-
tion using an HY zeolite bed material (25 wt% HY zeo-
2. PE, PP, and PS lite, 30 wt% bentonite, and 45 wt% inert alumina,
agglomerated by a wet extrusion method)18). This
PE and PP are lightweight, flexible, and water and fraction fulfils the European Union requirements for
chemical resistant polymers, and so are often employed commercial gasoline, and its research octane number
in packaging films and containers. In contrast, PS is (RON) index (96.5) is comparable to that of standard
lightweight, stiff, and thermally insulating, and thus is automotive fuel.
often used in containers and buffer materials. As pre- Pyrolysis is also effective for treating waste plastics.
viously mentioned, PE, PP, and PS (the 3Ps) are the The 3P are easily converted into gas, oil, and wax
major components of waste plastics, so the effective- fractions containing small quantities of char27),28).
ness of pyrolysis for treating these resins have been Investigation of the effects of HZSM-5 zeolite catalysts
extensively investigated. The 3Ps are pyrolyzed into on the pyrolysis of waste plastic mixtures (mixtures of
smaller hydrocarbons via breakage of the C _C back- HDPE, LDPE, PP, and PS containing traces of PET and
bone, allyl chain fission, intermolecular hydrogen PVC, from Slovenia, South-Taiwan, and Hungary)
abstraction, β-scission, hydrogen transfer, radical addi- found a significant increase in the aromatic fraction
tion, disproportionation, and radical recombination, as (BTX, ethylbenzene, and styrene)29). In addition,
summarized elsewhere3)5) . waste plastics, especially PE, PP, and PS, are good
The “Hamburg process” is a fluidized-bed pyrolysis resources for hydrogen production by catalytic steam
system (Fig. 1) in which the plastics are introduced reforming. The H2 yields from HDPE, PP, PS, and
into an auxiliary fluidized bed of quartz sand using a PE-rich mixed plastics were approximately 2.5, 2.6,
screw feeder or a double lock6). The pyrolysis gas is 1.7, and 2.0 L H2/g plastic, respectively, at a gasifica-
removed from the reactor, fine dust and soot are tion temperature of 800 using a Ni_Mg_Al catalyst
removed in a cyclone, then the gas is cooled to ambient prepared by co-precipitation30). The effects of various
temperature in a quencher using a cycle of product oil. types of Ni catalysts, such as Ni/Al2O3, Ni/MgO, Ni/
The gas is then passed through two quenching columns, CeO, Ni/ZSM-5, Ni/CeO2/Al2O3, Ni/CeO2/ZSM-5, Ni_
which are filled with glass bodies, and is condensed Al, Ni_Cu_Al, and Ni_Mn_Al were also evaluated in the
into oil. The exhaust gases are used to preheat the flu- plastic gasification process31)42) .
idizing gas by means of heat exchange. The Hamburg PE and PP can be decomposed into aromatic hydro-
process was investigated for the pyrolysis of mixed carbons using activated carbon impregnated with Pt, Fe,
plastics consisting of polyethylene (PE), polypropylene Mo, Zn, Co, Ni, and Cu. PE was converted into aro-
(PP), and polystyrene (PS) containing traces of polyvi- matic compounds with a maximum yield of 46.2 wt%
nyl chloride (PVC) at 730 7). This process yielded at 526 using 3 wt% Pt/C43)45) . The maximum

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–1 –1
Fig. 2 Pyrolysis Behavior of PVC: (a) TG and DTG Curves with Heating Rate between 0.5 min and 40 min ; (b) Selected
Ion Chromatogram of the Major Compounds at 4 min –1 52)

yield of aromatic compounds was ~30 wt% from PP at formed due to cyclization reactions in the first and sec-
502 using 3 wt% Pt/C. Other catalysts, such as Pt ond stages. Detailed mechanisms for the dehydro-
and Rh/Al2O346), Ga/ZSM-547), Ru/Al2O348),49), Pb, Co, chlorination and subsequent hydrocarbon formation
and Pb_Co/BaTiO350), Ni, Co, Fe, Mn, and Zn/AWBN during PVC pyrolysis were summarized previous-
(acid washed bentonite clay)51), have also been studied ly53),54).
for the catalytic pyrolysis of the 3P. These significant amounts of HCl formed during
Based on the numerous studies focusing on the pyrolysis result in the corrosion of treatment facilities,
pyrolysis of PE, PP, and PS, we concluded that 3P as previously mentioned. Additionally, the “Act on
waste can be converted into high value-added products the Promotion of Sorted Garbage Collection and
by this process, with new advances reported every year. Recycling of Containers and Packaging” specifies that
However, the presence of PVC and PET in 3P waste p y r o l y s i s o i l m u s t h ave a c h l o r i n e c o n t e n t o f
causes deterioration in the pyrolysis product quality, 100 p pm55),56). Thus, chlorine removal from plastic
together with corrosion and clogging of the treatment waste or pyrolysis products is necessary for the treat-
facilities. Overcoming these problems will be impor- ment of PVC-containing plastics.
tant in the future. The preferred option for Cl removal from PVC is
“dry treatment” by heating prior to liquefaction or gas-
3. PVC ification, which is categorized as “dehydrochlorination.”
The dehydrochlorination of PVC is a seemingly simple
PVC is strong, pliable, and flame resistant, which are reaction, expected to form only HCl and polyene struc-
ideal characteristics for use in films, pipes, and cable tures. However, as the extent of dehydrochlorination
materials. The most unique characteristic of PVC is increases and polyene structures become dominant, a
its high chlorine content, which accounts for 57 wt% of series of terminating reactions occur, such as cycliza-
pure PVC resin, and allows for high volumes of PVC to tion and crosslinking, locking the remaining chloride
be manufactured with relatively low amounts of hydro- within stable structures53),54). Removal of these isolated
carbon feedstock. chloride atoms is extremely difficult, so complete chlo-
The authors previously investigated the pyrolysis rine removal through only dry treatment is difficult.
behavior of PVC resin by combined thermogravimetry- To overcome this issue, the authors investigated the
mass spectroscopy (TG-MS)52), as shown in Fig. 2. steam-assisted dehydrochlorination of PVC under
The weight loss during PVC pyrolysis occurs in two atmospheric pressure57). Figure 3(a) shows the de-
stages, firstly at 200-350 , then above 350 . The hydrochlorination behavior of both pure PVC resin and
first stage corresponds mainly to dehydrochlorination, flexible PVC polymer in the presence and absence of a
resulting in the production of HCl and a solid residue flow of 50 vol% steam in N2, demonstrating that steam
with a polyene structure. In addition, the m/z36 in addition enhances dehydrochlorination. Infrared spec-
Fig. 2(b) corresponds to HCl, suggesting two-stage de- troscopy showed that the steam-treated samples exhibited
hydrochlorination, and implies that two different types a peak corresponding to an OH group at 3400 c m–1,
of bonds (e.g., head to head and head to tail) are de- suggesting that steam (H2O) acted as a nucleophile to
hydrochlorinated. PVC pyrolysis produced 52.9 wt% substitute Cl with an OH moiety. Thus, the presence
HCl during at 700 27),28), and 56.3 wt% HCl at 740 6). of steam enhanced dehydrochlorination.
Benzene and other aromatic hydrocarbons were also Dehydrochlorination using a single screw extruder

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Fig. 3 (a) Time Dependence of PVC Dehydrochlorination for Both Resin and Flexible PVC Samples Treated at 230 Both
with and without Steam; (b) FT-IR Spectra of Fresh and Dehydrochlorinated PVC Resin after Treatment for 60 min at
a Steam Concentration of 50 vol% at Various Temperatures57)

Fig. 4 Single-screw Extruder Employed in the Dehydrochlorination Experiments58)

was studied for municipal waste plastics (43 % PP, resin was dechlorinated at 190 in a 1.0 M NaOH/
29 % PE, 8 % PS, 7 % PVC, 1 % PVDC, 9 % PET, and ethylene glycol (EG) solution at atmospheric pressure,
3 % others) (Fig. 4)58). The plastic materials were resulting in 97.8 % dechlorination62). The effective-
then compressed (melted), metered (fixed feeding), and ness of this system was confirmed using flexible PVC
discharged. The lowest residual Cl content in the tubing, resulting in complete dechlorination61). Ball
treated sample (i.e., 0.27 wt%) was achieved at 375 mill-assisted dechlorination was also developed
with a feeding rate of 43.6 kg h–1, and a residence time (Fig. 5(b)), with enhanced dechlorination rate for both
of 94 s (feed screw: 75 rpm; discharge screw: 75 rpm). flexible and rigid PVC materials of 97 % and 84 %,
An alternative technique for Cl removal from PVC is respectively, compared to 80 % and 40 % in the absence
“wet treatment” prior to liquefaction or gasification, of ball milling (Figs. 5(c) and 5(d)). The Y2O3_ZrO2
which is otherwise known as “dechlorination.” The balls used have high mechanical strength, so are highly
authors previously reported that dechlorination of PVC durable for the milling process. The chlorine present
materials using an alkaline solution (Fig. 5(a)) pro- in the EG solution following dechlorination can be
gresses by two pathways, E2 elimination and SN2 sub- recovered by electrodialysis using either ion-exchange
stitution (Fig. 5(a))59)65 ). For example, pure PVC membranes66) or an alumina/zeolite membrane67),

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Fig. 5 Dechlorination of PVC Using NaOH/EG Solution60),62): (a) Simple Dechlorination System; (b) Ball-mill Assisted
Dechlorination System; (c) Dechlorination Behavior of Flexible PVC in the Presence and Absence of Ball-milling; (d)
Dechlorination Behavior of Rigid PVC in the Presence and Absence of Ball-milling

allowing simultaneous recovery of Cl and regeneration

of EG. Other combinations, such as NaOH/dimethyl
sulfoxide (DMSO)68) and ammonia solution69), have
also been reported, resulting in quantitative dechlorina-
tion. In addition, the SN2 substitution was also applied
for “PVC upgrading” using various nucleophiles70)78 ),
which can add new properties to PVC while maintain-
ing the basic PVC properties. For example, only
3.8 % of the Cl present in PVC was substituted with
isothiocyanate (_N C S) at 100 in tetrahydrofuran
(THF)/dimethyl sulfoxide (DMSO) solution, which
showed reduced adhesion of bacteria (Staphylococcus
capitis) by 79 % (Fig. 6)78). This finding may be very
important in the use of PVC in sanitary goods, wall-
paper, and so on.
Cl capture by solid absorbents during pyrolysis has
also been examined. The main studies discussing the
pyrolysis of PVC-containing plastics are summarized in
Table 1. Mixtures of PE/PP/PS/PVC (weight ratio
3/3/3/1) were pyrolyzed in the presence of a Ca _ C
absorbent, prepared by the calcination of mixtures of
90 wt% calcium carbonate (CaCO3) and 10 wt% phenol Fig. 6 Antibacterial Effect of PVC Substituted with Isothiocyanate
resin, using a two-step fixed bed reactor79). The liquid Groups78)
and gas yields were not affected by the presence of Ca_
C absorbent, giving yields of 67 wt% and 24 wt%,
respectively, compared to yields of 63 wt% and 24 wt% 5 equivalents of Ca_C were employed, so no Cl was
in the absence of Ca_C, due to blockage of Cl contami- detected following 4 repeated runs. Ca- and Fe-based
nation of the oil by the Ca_C absorbent. Approximately absorbents, synthesized by the calcination of mixtures

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Table 1 Summary of Previous Research on Catalytic Pyrolysis of PVC Plastics

Catalyst or
Authors Plasticsa) Equipmentc) and conditions Results
absorbentb)
Bhaskar et al.79) PE/PP/PS/PVC Ca_C Equipment Ø Thermal: Liquid 63 wt%, Gas 24 wt%,
(3/3/3/1) Amount: 4 g Two-step fixed bed reactor Residue 13 wt%, 360 ppm Cl in liquid
Amount: 10 g Conditions Ø Wi t h C a _ C : L i q u i d 67 w t % , G a s
Pyrolysis bed: 120 (hold 60 min) 23 wt%, Residue 10 wt%, 0 ppm Cl in
–1
(3 min ) 430 ; Catalyst liquid
bed: 350
Sakata et al.80) PVC/HIPS_Br Fe_C Equipment Ø Thermal: Liquid 48 wt%, Gas 21 wt%,
(4/1) Amount: 4 g Single-step fixed bed reactor Residue 31 wt%, 4300 ppm Cl and
Amount: 10 g Conditions 55000 ppm Br in liquid
Pyrolysis and catalyst bed: 120 Ø Wi t h F e _ C : L i q u i d 38 w t % , G a s
–1
(hold 60 min) (3 min ) 12 wt%, Residue 48 wt%, 0 ppm of Cl
430 and Br in liquid
PP/PE/PS/PVC/ Ca_C Ø Thermal: Liquid 71 wt%, Gas 17 wt%,
HIPS_Br Amount: 4 g Residue 12 wt%, 1120 ppm Cl and
(3/3/2/1/1) 7300 ppm Br in liquid
Amount: 10 g Ø Wi t h C a _ C : L i q u i d 66 w t % , G a s
25 wt%, Residue 9 wt%, 0 ppm of Cl
and Br in liquid
MPW Ca_C Ø Thermal: Liquid 60 wt%, Gas 25 wt%,
Amount: 10 g Amount: 4 g Residue 15 wt%, 1170 ppm Cl and
40 ppm Br in liquid
Ø Wi t h C a _ C : L i q u i d 60 w t % , G a s
25 wt%, Residue 15 wt%, 590 ppm Cl
in liquid
Brebu et al.82) PE/PP/PS/PVC/ CaCO3 Equipment Ø Liquid 59-67 wt%, Gas 17-20 wt%,
ABS_Br FeOOH Single-step fixed bed reactor Residue 13-17 wt%
(3/3/2/1/1) Ca_C Conditions Ø C l i n o i l : T h e r m a l (4972 p p m )
Amount: 10 g Fe_C Pyrolysis and catalyst bed: r.t. F e O O H (3370 p p m )F e _C
Dolomite (5 min –1) 450 (1014 ppm)C aCO3 (355 ppm)C a_
Amount: 10 g C (113 ppm)
Ø B r i n o i l : T h e r m a l (1924 p p m )
CaCO3 (1161 ppm)C a_C (418 ppm)
F e _C (170 p p m )F e O O H
(104 ppm)
Cho et al.83) MPW CaO Equipment Ø Liquid 60-62 wt%, Gas 30-31 wt%,
(Cl: 11300 ppm) Amount: 43 g Fluidized-bed reactor Residue 6-7 wt%
Amount: 800 g Ca(OH)2 Conditions Ø Cl in oil: Thermal (502 ppm)C aO
Amount: 28 g Bed temperature: about 710 (58 ppm)o yster shell (57 ppm)
Oyster shell Ca(OH)2 (55 ppm)
Amount: 76 g
a) Values in ( ) are weight ratio of mixtures
b) Ca_C: synthesized by calcination of 90 wt% CaCO3 and 10 wt% phenol resin; Fe_C: Synthesized by calcination of 90 wt% α-FeOOH and
10 wt% phenol resin.
c) Single-step fixed bed reactor: pyrolysis bed and catalyst bed are presence in a same furnace; Two-step fixed bed reactor: pyrolysis bed and
catalyst bed are located in separate furnaces.

of 90 wt% iron oxyhydroxide (FeOOH) and 10 wt% (n2 and 4) and FeCl2 in the used absorbents, which
phenol resin, were also evaluated for both PVC- implies that HCl gas is produced during PVC pyrolysis
containing plastics and brominated flame retardant- and is subsequently absorbed. In contrast, Ca _ C
containing plastics, such as high-impact polystyrene absorbent did not completely remove Cl from liquid
(HIPS_ Br)80). In all cases, liquid, gas, and residue products derived from municipal plastic wastes (MPW),
yields were not significantly affected by the use of Ca_ with approximately 590 ppm remaining. The MPW
C and Fe_C absorbents. Therefore, Ca_C and Fe_C contained PET and small quantities of acrylonitrile-
absorbents have no catalytic effect on the pyrolysis of butadiene-styrene (ABS) in addition to the 3P and PVC,
organic compounds, but completely removed both Cl so chlorinated organic compounds were formed, which
and Br from PE/PP/PS/PVC/HIPS_Br mixtures. In were difficult to remove using these absorbents81).
addition, X-ray diffraction (XRD) detected CaCl2_nH2O Therefore, complete removal of Cl and Br from ABS_

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Br and PVC-containing 3P is challenging. However,

FeOOH and Fe_C absorbents were effective in remov-
ing organic bromine from degradation oils, whereas Ca_
C and CaCO3 were most effective for chlorine remov-
al82). Calcium-based absorbents, such as CaO, calcium
hydroxide (Ca(OH)2), and oyster shell, removed Cl
from pyrolysis oil, resulting in only 55-58 ppm Cl com-
pared to 502 ppm in the absence of Ca-based absor-
bents83).

4. PET

PET is the most commonly used polyester resin for

the production of various items such as bottles, fibers,
sheets, and films, due to its high transparency, light Fig. 7 Benzene Yield and Purity in the Pyrolysis Oil Obtained at
Different Conditions105),109)111)
weight, chemical resistance, and gas barrier properties.
PET bottles are made of high-purity PET resin with few
additives, which allows direct mechanical recycling.
In addition, various solvolysis techniques such as
hydrolysis84)88 ), methanolysis89)91 ), glycolysis92)94 ),
and aminolysis95)97 ) allow PET decomposition into
monomers. The main advantage of solvolysis is the
recovery of monomers at a relatively low temperature.
However, the presence of metals, additives, and other
resins in PET obstruct frequent recycling of the solvent
without regeneration.
Pyrolysis allows the avoidance of solvent use, but
PET produces high boiling point organic acids such as
terephthalic acid (TPA) and benzoic acid (BA), along Fig. 8 Scheme of Benzene Production during Pyrolysis of PET/
with a large amount of carbonaceous residues during Ca(OH)2 Mixture
pyrolysis98)101 ), which cause corrosion and clogging of
the treatment facilities58). FeOOH catalysts decom-
pose these sublimating products into acetophenone, Initially, calcium hydroxide is decomposed into CaO
benzene, and phenol rich oils102),103). In addition, oil and steam, followed by hydrolysis of PET by steam
production from PP/PET mixtures was increased by derived from Ca(OH)2, producing TPA. The produced
TiO2/SiO2 catalysts due to hydride abstraction from PP TPA and CaO formed calcium terephthalate (CaTP),
pyrolysates on the Lewis acid sites onto PET pyroly- which subsequently decomposed into benzene and CO2
sates on the catalyst, which broke the PET down into via decarboxylation of the TPA carboxyl group and de-
lighter hydrocarbons via β-scission104). carbonation of CaCO3. The resulting CaO can then be
The authors have also reported the conversion of PET recycled for the decarboxylation of TPA.
into benzene-rich oil during pyrolysis in the presence of Other metal hydroxides, such as aluminum hydrox-
Ca(OH)2, CaO, and steam105)113 ). Benzene is one of ide (Al(OH)3), magnesium hydroxide (Mg(OH)2),
the most important petrochemical feedstocks, and the Ca(OH)2, and barium hydroxide (Ba(OH)2), were eval-
high abundance of limestone resources in Japan favors uated for benzene production107). Benzene production
such a process. Benzene yield and purity in the pyrol- was mainly affected by catalyst basicity, resulting in
ysis oil obtained under different conditions are summa- high benzene yield of 81 % and purity of 90 wt% in the
rized in Fig. 7. Benzene yield and purity are only presence of Ca(OH)2 and Ba(OH)2. The effectiveness
23 % and 30 wt%, respectively, in the absence of addi- of benzene production using Ca(OH)2 was confirmed
tives (Entry 1). The mixture of PET/CaO improved for both pure PET resin, and for metals and additives
the yield and purity because decarboxylation of TPA is containing PET wastes, resulting in comparable yields
promoted (Entry 2). Furthermore, the mixture of PET/ and compositions of product oils and gases from low-
Ca(OH)2 significantly enhanced both yield and purity to purity PET wastes114). PET incorporated into 3P plas-
88 % and 79 wt%, respectively (Entry 3)105). This pro- tics can also be converted into benzene using a hard
cess was carried out at 700 using a Ca(OH)2/PET burnt lime fluidized bed without TPA production108).
molar ratio of 10. The benzene production process In contrast, TPA was present in the wax fraction derived
from PET/Ca(OH)2 mixture is summarized in Fig. 8. from experiments using quartz sand.

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in the samples had no negative influence on benzene

production113),114).

5. Conclusion

This review summarized a number of studies of the

pyrolysis of PE, PP, PS, PVC, and PET. The main re-
search trend in plastic pyrolysis concentrates on PE, PP,
and PS, which account for ~70 % of total plastic pro-
Fig. 9 Scheme of Two-step Process for Benzene Production from
PET duction. The research trend has gradually shifted to
catalytic pyrolysis systems, such as catalyst develop-
ment, to improve both the yield and quality of pyrolysis
The authors also reported a two-step process for ben- oils and gases. The studies discussed in this review
zene production from PET waste using a CaO fixed were mainly on the laboratory scale, but demonstrate
bed109) 113). This process can recover metals separately the great potential for obtaining high quality oils and
from benzene-rich oil by dividing the processes into gases, which can substitute for natural oil and gas.
steam decomposition of PET-metal composites and de- In contrast, the pyrolysis of PVC and PET has re-
carboxylation of TPA using CaO (Fig. 9). Initially, ceived less attention compared to 3P due to the difficulty
the PET-metal composites are hydrolyzed by steam into in recovering useful products. In addition, these mate-
gaseous TPA, whereas the metals remain in solid form. rials are converted into harmful compounds during
The gaseous TPA is then passed through a CaO fixed pyrolysis, which cause a number of issues, including
bed, resulting in selective conversion to benzene. The deterioration in the quality of the pyrolysis products.
one-step process in the presence of Ca(OH)2 (Fig. 7, Therefore, waste plastics containing high amounts of
Entry 3) shows the highest benzene yield because of the PVC and PET are commonly avoided in current feed-
excellent contact between PET and Ca(OH)2 during stock recycling systems, despite the main components
decomposition. However, the high temperature of of 3P in the waste. Thus, the increase in recycling
700 simultaneously induces pyrolysis of PET, result- rates in terms of feedstock recycling has slowed.
ing in lower benzene purity compared with the oils ob- These issues with PVC and PET during pyrolysis must
tained from the two-step process (Fig. 7, Entries 4-7). be solved to promote recycling rates of municipal plas-
The benzene yield of 48 % and purity of 78 wt% ob- tic wastes while maximizing product quality. The
tained at hydrolysis temperature of 450 and CaO bed studies in this review, including the author’s own work,
temperature of 700 (Fig. 7, Entry 4) are improved at describe the key developments in the treatment of PVC-
lower temperatures, resulting in 64 % yield and 83 wt% and PET-containing plastic wastes, which will be im-
purity (Fig. 7, Entry 5). Maximum benzene yield of portant for the development of future recycling systems.
74 % and purity of 97 wt% were obtained from PET Progress in both plastic recycling and the development
resin by managing the temperatures of both hydrolysis of recycling techniques should be accelerated to ensure
c h a m b e r a n d C a O b e d ( F i g . 7, E n t r y 6) 110). the conservation of resources along with a sustainable
Furthermore, maximum benzene yield of 84 % and economy due to the finite nature of fossil fuels.
99 w t% purity were achieved for the oil produced
from TPA (Fig. 7, Entry 7)111). The authors also References
applied this process for the recovery of incorporated
metals from X-ray films and magnetic tape and 1) Plastic Waste Management Institute, Plastic Products, Plastic
Waste and Resource Recovery [2014], [Link]
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the magnetic tape contained maghemite (γ-Fe2O3), and 2) 16514 of chemical goods in 2014, The Chemical Daily Co.,
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