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Synergistic Effect and Chlorine-Release Behaviors During Co-pyrolysis of

LLDPE, PP, and PVC

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DOI: 10.1021/acsomega.9b04116

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Synergistic Effect and Chlorine-Release Behaviors During Co-

pyrolysis of LLDPE, PP, and PVC
Zhilong Yuan, Jing Zhang, Peitao Zhao,* Zheng Wang, Xin Cui, Lihui Gao, Qingjie Guo,
and Hongjing Tian
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ABSTRACT: Plastic wastes are environmentally problematic and

costly to treat, but they also represent a vast untapped resource for the
renewable chemical and fuel production. Pyrolysis has received
extensive attention in the treatment of plastic wastes because of its
Downloaded via 91.132.36.27 on January 5, 2022 at 12:35:44 (UTC).

technical maturity. A sole polymer in the waste plastic is easy to recycle

by any means of physical or chemical techniques. However, the
majority of plastic in life are mixtures and they are hard to separate,
which make pyrolysis of plastic complicated compared with pure
plastic because of its difference in physical/chemical properties. This
work focuses on the synergistic effect and its impact on chlorine
removal from the pyrolysis of chlorinated plastic mixtures. The
pyrolysis behavior of plastic mixtures was investigated in terms of
thermogravimetric analysis, and the corresponding kinetics were
analyzed according to the distributed activation energy model
(DAEM). The results show that the synergistic effect existed in the pyrolysis of a plastic mixture of LLDPE, PP, and PVC, and
the DAEM could well predict the kinetics behavior. The decomposition of LLDPE/PP mixtures occurred earlier than that of
calculated ones. However, the synergistic effect weakened with the increase of LLDPE in the mixtures. As for the chlorine removal,
the LLDPE and PP hindered the chlorine removal from PVC during the plastic mixture pyrolysis. A noticeable negative effect on
dechlorination was observed after the introduction of LLDPE or PP. Besides, the chlorine-releasing temperature became higher
during the pyrolysis of plastic mixtures ([LLDPE/PVC (1:1), PP/PVC (1:1), and LLDPE/PP/PVC (1:1:1)]. These results imply
that the treatment of chlorinated plastic wastes was more difficult than that of PVC in thermal conversion. In other words, more
attention should be paid to both the high-temperature chlorine corrosion and high-efficient chlorine removal in practical. These data
are helpful for the treatment and thermal utilization of the yearly increased plastic wastes.

1. INTRODUCTION operating parameters such as temperature or heating rate.3−6

Plastic is visible in both agricultural and industrial areas, small The chlorine was commonly removed from plastic mixtures
to everyday items, and large to aerospace equipment. It plays before the pyrolysis step.7 Miranda et al.,8 stated that the
an irreplaceable role in people daily lives. According to chlorine in polyvinyl chloride (PVC) could be completely
statistics, the annual global plastic production had sharply risen removed at a temperature of 375 °C, and the synergistic effect
from 2 million tons in 1950 to 348 million tons in 2017, of during the co-pyrolysis of PS and PVC was also observed in
which 17.7% in NAFTA, 4% in Latin America, 18% in Europe, their work. Wu et al.,9 observed the inhibition between
7.1% in Middle East Africa, 2.6% in CIS, and 50.1% in Asia polyethylene (PE) and PVC during co-pyrolysis. Many
(29.4% in China, 3.9% in Japan, and 16.8% in Rest of Asia).1 researchers studied on the pyrolysis kinetics for the reactor
In the meanwhile, the global production of plastic wastes design and process optimization. Aboulkas et al.,10 reported
reached 6 billion tons in 2015, of which 76% were landfilled, that the pyrolysis of PE and polypropylene (PP) could be
12% were burnt, 3% entered the ocean, and only 9% were characterized by the one-step model, and the activation energy
recycled.2 It has been a serious threat to the human being
living environment because of the huge amount and ineffective Received: December 5, 2019
treatment. Thus, it was necessary to find a feasible way to Accepted: April 3, 2020
address plastic waste issues and to relieve environmental stress. Published: May 15, 2020
The pyrolysis has been received extensive attention because
of its flexibility to generate a combination of solid, liquid, and
gaseous products in different proportions only by varying the

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Table 1. Proximate and Ultimate Analysis of Materials

ultimate analysis (wt %a) proximate analysis (wt %a)
samples C H O N S Cl M Ash VM FC
LLDPE 85.61 14.29 0.02 0.05 0.03 0.00 0.02 0.05 99.86 0.07
PP 85.71 14.18 0.04 0.03 0.04 0.00 0.03 0.04 99.90 0.03
PVC 37.78 4.83 0.36 0.14 0.16 56.73 0.01 0.00 96.52 3.47
a
On an air dry base; M, inherent moisture; VM, volatile matter; and FC, fixed carbon.

of PE and PP fluctuated slightly at the conversion rate of 0.1− 800 °C under the nonisothermal conditions at a constant rate
0.9. However, Xu et al.,11 stated that the pyrolysis behavior of of 10, 20, 30, and 40 K/min. The plastic mixtures were
low-density polyethylene (LDPE) and PP could be accurately prepared by mixing PP, LLDPE, and PVC, according to
described by the R2 (shrink ball) and R3 (contracted cylinder) various proportions as shown in Table 2.
models while the first and second stages of PVC pyrolysis
belonged to A3 (three-dimensional nucleation) and D3 (three- Table 2. Composition of Plastic Mixturesa
dimensional diffusion) models. Qiao et al.,12 believed that the
frequency factor and activation energy presented the same heating rate (K/min)
variation trend. Soria-Verdugo et al.,13 found that the kinetics no. samples mixing ratio 10 20 30 40
parameters evaluated by Ozawa−Flynn−Wall and Kissinger− 1 LLDPE √ √ √ √
Akahira−Sunose methods were similar to the distributed 2 PP √ √ √ √
activation energy model (DAEM). Some other works 3 PVC √ √ √ √
investigated on the co-pyrolysis of plastics, mainly focusing 4 LLDPE/PP 1/1 √ √ √
on the oil quality.14,15 All these works have made great 5 LLDPE/PP 1/2 √ √ √
contributions to the understanding of plastic pyrolysis 6 LLDPE/PP 1/3 √ √ √
behaviors and oil quality. However, the synergistic effect 7 LLDPE/PP/PVC 3/2/1 √ √ √
during pyrolysis and its impact on chlorine removal are still 8 LLDPE/PVC 1/1 √
required to explore. In practical, the chlorine removal is quite 9 PP/PVC 1/1 √
important for the chlorinated organic wastes because of the 10 LLDPE/PP/PVC 1/1/1 √
acidic corrosion to equipment and environmental pollution, a
√ parameters utilized in the pyrolysis of plastic mixture; not
resulting from the dioxin formation. applicable.
In this work, the pyrolysis behaviors and kinetics of plastic
mixture of linear LLDPE, PP, and PVC were investigated by
2.3. Kinetics Analysis. The DAEM was based on the
thermogravimetric analysis (TGA) under various heating rates.
hypothesis of infinite parallel reaction and the activation energy
The kinetics parameters were derived according to the DAEM.
distribution. It could be written as follows12,16
∞i i i −E y yzy
jj
jjj1 − expjjjj− A τ × expjjj τ zzzdτ zzzzzzz × V *
The synergistic effects during the plastic mixture pyrolysis were

k RT { {z{
studied, and its impact on the chlorine removal was also τ

k k
V
discussed. This study is helpful for the harmlessness treatment V*
= ∫0 ∫0
and thermal utilization of plastic waste, especially the organic
chlorinated wastes. × f (E)dE (1)
Vvolatile matter at a given time, %; V*total volatile
2. MATERIALS AND METHODS matter, %; Tpyrolysis temperature, K; Eτ−activation
2.1. Material Preparation. Three typical plastics, energy at a given time (τ); Aτactivation energy at a given
including linear LLDPE, PP, and PVC, were obtained from time (τ); Eactivation energy, kJ/mol; Afrequency factor,
Exxon Corporation, China Petroleum and Chemical Corpo- 1/min; and gas constant, R = 8.314 kJ/(mol·K). f(E) was a
ration Maoming Branch, and Hanwha. Their density were 0.93, function of the activation energy E and met the conditions
0.98, and 1.41 g/cm3, respectively. There was no long chain ∞
branch in the structure of LLDPE compared to LDPE but ∫0 f (E)dE = 1
(2)
more short branches compared to HDPE. All the materials
were dried in an electric oven at ∼70 °C for 24 h to eliminate
∞i i −E y yyz
Eq 1 could be then simplified as
jj jij
jjjexpjj− A τ × expjjj τ zzzdτ zzzzzzz
the influence of moisture and utilized as it was without further

k RT { {z{
τ

k k
V
purification. The powdered samples with a diameter of around 1−
V*
= ∫0 ∫0
100 mesh were used for TGA. The proximate and ultimate
analysis of samples is presented in Table 1.
× V * × f (E)dE (3)
2.2. Pyrolysis Behavior. The pyrolysis was carried out in a
TG analyzer (LabsysEvo, SETARAM). Before the experiments, The pyrolysis temperature (T) at a given time (τ) could be
the crucible made of Al2O3 was placed in a muffle furnace at expressed by the heating rate β as follows
900 °C for 1 h to reduce experimental errors. The inner tube of T = T0 + βτ (4)
the thermogravimeter was flushed using a large flow rate of

i β y i −E zy i AR y
nitrogen (99.999%) for approximately 20 s. For each run, the Equation 3 was then derived as

lnjjj 2 zzz = jjj zz × + lnjjj zzz + 0.6075

sample mass was around 20 ± 0.5 mg, and the nitrogen flow

kT { k R { T k E {
1
rate was 20 mL/min. All the tests followed the same
procedure: steady at 30 °C for 5 min and then heated up to (5)

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Equation 5 fulfills the format of Y = aX + b, in which Y and X and then started to decompose at 460 and 434 °C,
are ln(β/T2) and 1/T, respectively. a is the slope, and b is the respectively. At this stage, LLDPE and PP began to decompose
intercept of the fitting line of ln(β/T2) versus 1/T. According because of the random chain scission, resulting in a loss of
to the TGA data, the activation energy (E) and frequency polymer molecular weight. The pyrolysis products were mainly
factor (A) could be obtained by E = −Ra and A = exp(b − macromolecular with small amount of volatile gases at this
0.6075) × E/R, respectively. stage. These macromolecular products could be further
decomposed by heating.17,18 Additionally, the temperature
3. RESULTS AND DISCUSSION (TP) for maximum weight loss rate occurred at 483 and 467 °C
3.1. Pyrolysis Behaviors of LLDPE, PP, and PVC. Table for LLDPE and PP, respectively, suggesting a higher thermal
3 summarizes the characteristic parameters of the pyrolysis of stability of LLDPE than PP. This was because the high number
of tertiary carbon existed in the molecule chain of PP, which
Table 3. Pyrolysis Parameters of Individual Components at provided more stable-free radicals than secondary of primary
Different Heating Ratesa carbon. In other words, higher branching degree of PP
(compared to LLDPE) resulted in a weaker link in the
heating rate DTGp Tp Ti Tf
polymers (K/min) (%/K) (°C) (°C) (°C) molecular chain of PP. Thus, the PP was easier than LLDPE to
LLDPE 10 −3.55 483 460 505 decompose. Besides, some secondary condensation reactions
30 −2.84 505 482 534 could also happen during the pyrolysis. Liu et al.,17 observed
40 −2.39 511 490 544 an exothermic peak at the later stage of LLDPE and PP
PP 10 −2.93 467 434 489 pyrolysis.
30 −2.47 487 451 521 Contrary to LLDPE and PP, the pyrolysis of PVC could be
40 −2.17 492 463 529 clearly divided into two stages as dehydrochlorination with the
PVCb 10 Stage 1 −1.37 288 272 379 temperature range of 272−379 °C and the hydrocarbon
Stage 2 −0.36 467 379 556 decomposition at the temperature range of 379−556 °C at the
30 Stage 1 −1.06 316 294 404 heating rate of 10 K/min. This was because the chlorine was
Stage 2 −0.31 489 404 563 usually removed from plastic mixtures prior to the pyrolysis
40 Stage 1 −0.93 326 300 415 step.7 The DTGP at 288 °C was significantly higher than that
Stage 2 −0.30 498 415 573 at 467 °C, indicating that the decomposition of PVC mainly
a
Ti: the temperature at the TG value of 95% was defined as the initial appeared at the first stage. At this stage, the main products
decomposition temperature of the pyrolysis. Tf: the final temperature were hydrogen chloride (HCl) and a small amount of gases
of the pyrolysis. Tp: the maximum mass loss rate temperature. DTGp: with small molecules (e.g., hydrogen, methane, ethane,19 and
the maximum mass loss rate. bFor samples containing PVC, the Ti at ethylene9,20). The categories of products at the second
stage one was defined as chlorine-release temperature, referring to pyrolysis stage were very complicated, mainly derived from
yuan et al.,19 the pyrolysis of polyene-conjugated structure in PVC at high
temperatures. The main products from this stage consisted of
individual polymers (LLDPE, PP, and PVC) under various aliphatic compounds, aromatic compounds (benzene, toluene,
nonisothermal heating rates as 10, 30, and 40 K/min, o-xylene, chlorobenzene, etc.), and chars.21,22
respectively. The thermogravimetry/ derivative thermogravim- LLDPE, PP, and PVC presented a similar feature in the
etry (TG/DTG) data are presented in Figure S1. Both LLDPE aspect of the pyrolysis parameters. The initial (Ti) temper-
and PP presented a similar pyrolysis behavior with only one ature, maximum weight loss (Tp), and final temperatures (Tf)
reaction stage, which could be ascribed to their similar of LLDPE, PP, and PVC moved to higher temperatures with
chemical structure. This was consistent with those reported by the heating rate (increasing from 10 to 40 K/min). In the
Aboulkas et al.,10 and Xu et al.,.11 At the heating rate of 10 K/ meanwhile, the DTGP values became lower with the heating
min, both LLDPE and PP were melted at a low temperature rates, which could be attributed to thermal lag and heat

Table 4. Pyrolysis Parameters of Plastic Mixtures at Various Heating Rates

polymers heating rate (K/min) DTGp (%/K) Tp (°C) Ti (°C) Tf (°C)

LLDPE:PP(1:1) 10 −3.31 471 441 494
30 −2.83 493 466 522
40 −2.32 498 469 534
LLDPE:PP(1:2) 10 −3.05 469 435 493
30 −2.62 491 456 521
40 −2.26 497 465 530
LLDPE:PP(1:3) 10 −2.81 466 427 491
30 −2.54 489 455 520
40 −2.20 499 464 532
LLDPE:PP:PVC(3:2:1) 10 Stage 1 −0.23 305 305 376
Stage 2 −2.58 479 376 507
30 Stage 1 −0.18 342 324 396
Stage 2 −2.29 500 396 532
40 Stage 1 −0.13 348 337 418
Stage 2 −1.95 507 418 540

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Figure 1. Experimental and calculated TG/DTG curves of plastic mixture (PE = LLDPE, 10 K/min).

transfer limitations. The temperature difference between the weakened with the increase of LLDPE in the mixtures. At a
furnace and samples was more and more noticeable with the given temperature, the experimental TG values were lower
heating rates. Besides, the pyrolysis reactions also depended on than that of theoretical calculation. It indicates that the
the heating rates. The DTGP values started decreasing, individual components interacted each other during the
indicating a lower decomposition rate for LLDPE and PP pyrolysis of LLDPE with PP, which played a synergistic effect
and a lower chlorine removal and decomposition rate for PVC. on the pyrolysis reaction.
3.2. Pyrolysis of Plastic Mixtures. Table 4 presents the In each case, the peaks of the experimental DTG curves
basic data from the pyrolysis of plastic mixtures. These moved to low temperatures compared to the theoretical ones.
parameters were quite different from those for sole plastic The corresponding peak values of the experimental DTG
pyrolysis. For LLDPE/PP mixtures, the initial decomposition curves were higher than that from linear calculation, indicating
temperature (Ti) and the maximum mass loss rate temperature that the LLDPE/PP mixtures had lower thermal stability
(TP) decreased at a heating rate of 10 K/min, when the mass during the co-pyrolysis of LLDPE with PP.
ratio of LLDPE to PP was decreased from 1:1 to 1:3. This For LLDPE/PP/PVC (3:2:1), a higher initial temperature
indicates that the thermal stability of the LLDPE/PP mixtures was observed compared to that of theoretical calculation,
tended to reduce with the PP proportion in the mixture. indicating the postpone of the LLDPE/PP/PVC (3:2:1)
The pyrolysis of LLDPE/PP/PVC (3:2:1) could be divided pyrolysis. It also suggests that the chlorine release from PVC
into two main reaction stages. The first DTGP value of moved toward higher temperatures. The experimental DTG
LLDPE/PP/PVC mixture was lower than the PVC pyrolysis curves of LLDPE/PP/PVC (3:2:1) pyrolysis showed higher
while it became higher at the second stage. The first stage was peak temperature as well as lower peak value at the first stage
mainly ascribed to the chlorine removal. However, the compared to that of calculated ones. This implies that the
pyrolysis of LLDPE/PP/PVC (3:2:1) would be mainly LLDPE/PP/PVC (3:2:1) had higher thermal stability during
characterized by the pyrolysis of LLDPE and PP as the the pyrolysis. It could also conclude that the pyrolysis of
temperature was above 427 °C because of the low PVC (1/6) LLDPE/PP/PVC (3:2:1) led to a deceleration of the chlorine
proportion in the mixture. The initial decomposition temper- release from PVC. At the second stage, the difference between
ature (Ti) of polymers followed the order of LLDPE > the experimental and the calculated TG/DTG curves indicated
LLDPE/PP (1:1) > LLDPE/PP (1:2) > PP > LLDPE/PP an unnoticeable antagonistic during the LLDPE/PP/PVC
(1:3) > LLDPE/PP/PVC (3:2:1) > PVC, indicating the (3:2:1) pyrolysis. Besides, the pyrolysis reactions at the second
highest thermal stability of LLDPE. stage were mainly composed of LLDPE with PP decom-
Figure 1 shows the experimental and theoretical TG/DTG position because of the low proportion of PVC in the LLDPE/
curves of the LLDPE/PP (1:1), LLDPE/PP (1:2), LLDPE/PP PP/PVC (3:2:1) mixture. Thus, the co-pyrolysis of LLDPE
(1:3), and LLDPE/PP/PVC (3:2:1) pyrolysis under the and PP was hindered after the introduction of PVC.
heating rate of 10 K/min. It is worth pointing out that the 3.3. Chlorine-Removal Behavior. The co-pyrolysis
theoretical curves were obtained from the linear combination plastic had a significant impact on the behavior of chlorine
of individual components. The obvious difference could be removal. To further investigate the synergistic effect, the PVC
observed between the experimental and theoretical TG/DTG was mixed with LLDPE and PP at various mass ratios and then
curves as shown in Figure 1. For LLDPE/PP mixtures, the pyrolyzed under the heating rate of 20 K/min. The
pyrolysis occurred earlier in practical, implying the promotion experimental and calculated TG/DTG curves are presented
of the mixtures pyrolysis. However, the synergistic effect in Figure 2. An obvious deviation between the experimental
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Figure 2. Experimental and theoretical TG/DTG curves of LLDPE/PVC (1:1), PP/PVC (1:1), and LLDPE/PP/PVC (1:1:1) (PE = LLDPE, 20
K/min).

Figure 3. Chlorine-removal efficiency of LLDPE/PVC (1:1), PP/PVC (1:1), and LLDPE/PP/PVC (1:1:1) at the first stage of co-pyrolysis (PE =
LLDPE, 20 K/min).

and the theoretical TG/DTG curves was observed for LLDPE/ (1:1:1), suggesting that the chlorine release was postponed in
PVC (1:1), PP/PVC (1:1), and LLDPE/PP/PVC (1:1:1), the pyrolysis. Additionally, the experimental TG values at a
indicating that a strong interaction occurred at the
given temperature were relatively higher than that of
dechlorination stage of the plastic mixture pyrolysis.
The pyrolysis occurred lately than the theoretical ones for theoretical values in all the cases, indicating an antagonistic
LLDPE/PVC (1:1), PP/PVC (1:1), and LLDPE/PP/PVC effect during the plastic mixture pyrolysis.
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Figure 4. Activation energy (E) and lnA of LLDPE, PP, PVC, and their mixtures within the conversion range of 0.1−0.9 (PE = LLDPE).

Figure 2 shows the higher peak temperature and the lower 3−12 wt % stayed in liquid, and only ∼2 wt % in char. Besides,
peak value of the experimental DTG curves at the first stage of the chlorine content of the liquid products depended on the
the LLDPE/PVC (1:1), PP/PVC (1:1), and LLDPE/PP/PVC type of plastic added, suggesting that there were reactions
(1:1:1) pyrolysis, showing a higher thermal stability of the between the products from the PVC degradation and those
plastic mixtures. The decomposition of the second stage was from the degradation of the other plastics. To some extent,
slightly delayed in the pyrolysis of plastic mixtures. Tang et these reactions would promote or hinder the chlorine removal,
al.,23 analyzed the chlorine balance and concluded that about which could be presented as the variation of the initial
88−96 wt % of chlorine would be released in the form of HCl, decomposition temperature and also the decomposition rate.
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The results here show that the other plastic would hinder the decomposition of the LLDPE/PP mixtures occurred earlier
chlorine removal from chlorinated waste plastics. In other than that of calculated ones. However, the synergistic effect
words, the treatment of chlorinated waste plastics became weakened with the increase of LLDPE proportion in the
more difficult than that of PVC in thermal conversion, and mixtures.
more attention should be paid on the high-temperature For the mixtures containing PVC, the dechlorination
chlorine corrosion in practical. temperature was delayed after introduction of the LLDPE
The dechlorination efficiency ψ at the first stage was and PP. In the meanwhile, the PVC dechlorination ratio was
estimated by ψ = Clrelease/Cltotal based on TG data. The hindered after introduction of LLDPE or PP. It suggests that
experimental and theoretical dichlorination efficiencies are the treatment of chlorinated waste plastics was more difficult
presented in Figure 3. Both LLDPE/PVC (1:1) and PP/PVC than that of PVC in thermal conversion. In practical, more
(1:1) showed a lower experimental dechlorination efficiency attention should be paid on both the high-temperature
compared to that of calculated ones. This suggests a noticeable chlorine corrosion and high-efficient chlorine removal. These
antagonistic effect on dechlorination during the co-pyrolysis of data are helpful for the treatment and thermal utilization of the
PVC with LLDPE or PP. Similarly, the deviation between the yearly increased plastic wastes.
experimental and theoretical dechlorination efficiency also
showed an antagonistic effect on dechlorination for LLDPE/
PP/PVC (1:1:1). Thus, all these results suggested that the
■
*
ASSOCIATED CONTENT
sı Supporting Information
treatment of chlorinated waste plastics was more difficult than The Supporting Information is available free of charge at
that of PVC in thermal conversion. https://pubs.acs.org/doi/10.1021/acsomega.9b04116.
3.4. Kinetics Behavior. Figure S2 shows the fitting curves
according to eq 5. The corresponding correlation coefficients Composition of TG/DTG curves, fitting curves, fitting
(R2) are summarized in Table S1. The values of R2 exceeded correlation coefficient value R2, activation energy values,
0.98 in the all cases, with the exception of PP (0.97) and and frequency factor values (PDF)
LLDPE/PP/PVC (3:2:1) (0.96) at the conversion of 0.1. It
indicates that the DAEM method could well predict the
kinetics behavior of the polymer pyrolysis. The kinetics
■ AUTHOR INFORMATION
Corresponding Author
parameters (E and A) are found in Tables S2 and S3. Peitao Zhao − School of Electrical and Power Engineering,
Figure 4 shows the variation of the activation energy (E) and China University of Mining and Technology, Xuzhou 221116,
lnA at the conversion range of 0.1−0.9 for LLDPE, PP, PVC, PR China; orcid.org/0000-0001-7834-387X; Phone: +86-
and their mixtures. The activation energy (E) of LLDPE and 516-2000; Email: [email protected], p.zhao@
PP fluctuated in the range of 215−229 and 199−215 kJ/mol, cumt.edu.cn
respectively. Unlike LLDPE and PP, PVC showed two reaction
stages as dechlorination and depolymerization, which had an Authors
activation energy (E) of 102−147 and 211−272 kJ/mol, Zhilong Yuan − School of Electrical and Power Engineering,
respectively. The bonding energy of the C−Cl was lower than China University of Mining and Technology, Xuzhou 221116,
that of C−C.9 The activation energy (E) of the first stage was PR China
lower than that of the second stage, resulting from the unstable Jing Zhang − School of Electrical and Power Engineering, China
structure of PVC at a temperature above 200 °C. The two University of Mining and Technology, Xuzhou 221116, PR
stages of PVC pyrolysis were corresponding to the breaking of China
C−Cl and C−C bonds. Zheng Wang − School of Electrical and Power Engineering,
For LLDPE/PP mixtures, the activation energy (E) kept China University of Mining and Technology, Xuzhou 221116,
reducing with the decrease of the initial mass ratio of LLDPE PR China
to PP at the same conversion rate. This was because of the Xin Cui − School of Electrical and Power Engineering, China
relatively low activation energy of PP. For LLDPE/PP/PVC University of Mining and Technology, Xuzhou 221116, PR
(3:2:1), the pyrolysis of LLDPE/PP/PVC (3:2:1) was mainly China
characterized by the pyrolysis of both LLDPE and PP because Lihui Gao − School of Environment Science and Spatial
of their share in the mixture after chlorine removal. Thus, Informatics, China University of Mining and Technology,
higher activation energy (E) was observed after the conversion Xuzhou 221116, PR China
rate of 0.1. Additionally, a similar feature of the kinetics Qingjie Guo − State Key Laboratory of High-efficiency
behavior was observed for LLDPE, PP, PVC, and their Utilization of Coal and Green Chemical Engineering, Ningxia
mixtures. The variation of the activation energy (E) showed University, Yinchuan 750021, PR China
the same trend as that of lnA. The maximum activation energy Hongjing Tian − State Key Laboratory Base of Eco-chemical
(E) as well as lnA was observed at the same conversion rate. It Engineering, College of Chemical Engineering, Qingdao
could be explained by the kinetics compensation effect, University of Science & Technology, Qingdao 266042, PR
indicating the linear relationship between the activation China; orcid.org/0000-0001-7855-2129
entropy of the activated body and the activated enthalpy.24 Complete contact information is available at:
https://pubs.acs.org/10.1021/acsomega.9b04116
4. CONCLUSIONS
Pyrolysis of plastics (LLDPE, PP, and PVC) and their mixtures Author Contributions
was conducted under non-isothermal conditions to investigate P.Z. and Q.G. conceived and designed the experiments; Z.Y.
the synergistic effect and its impact on chlorine removal from and H.T. performed the experiments; X.C. and L.G. performed
chlorinated plastics. The TGA data clearly indicated the theoretical study; Z.W. analyzed the data; P.Z., Z.Y., and J.Z.
synergistic effect during the pyrolysis of plastic mixtures. The wrote the paper.
11297 https://dx.doi.org/10.1021/acsomega.9b04116
ACS Omega 2020, 5, 11291−11298
 ACS Omega http://pubs.acs.org/journal/acsodf Article

Funding (19) Yuan, G.; Chen, D.; Yin, L.; Wang, Z.; Zhao, L.; Wang, J. Y.
This work was supported by the National Natural Science High efficiency chlorine removal from polyvinyl chloride (PVC)
Foundation of China (grant no. 51706240), the Foundation of pyrolysis with a gas−liquid fluidized bed reactor. Waste Manag. 2014,
34, 1045−1050.
State Key Laboratory of High-efficiency Utilization of Coal and (20) López, A.; de Marco, I.; Caballero, B. M.; Laresgoiti, M. F.;
Green Chemical Engineering (grant no. 2018-K02), and the Adrados, A. Dechlorination of fuels in pyrolysis of PVC containing
China Scholarship Council ([2018]5046, International Clean plastic wastes. Fuel Process. Technol. 2011, 92, 253−260.
Energy Talent Program 2018). (21) Tian, Y. Y.; Xie, K. C. Application of Py/FTIR to pyrolysis of
Notes PVC. J. Fuel Chem. Technol. 2002, 30, 569−572.
(22) Yu, J.; Sun, L.; Ma, C.; Qiao, Y.; Yao, H. Thermal degradation
The authors declare no competing financial interest. of PVC: A review. Waste Manag. 2016, 48, 300−314.

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