Waste Management xxx (2016) xxx–xxx

Contents lists available at ScienceDirect

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

Pyrolysis of waste tires: A modeling and parameter estimation study

Ò
using Aspen Plus
Hamza Y. Ismail a, Ali Abbas b, Fouad Azizi a, Joseph Zeaiter a,⇑
a
Department of Chemical and Petroleum Engineering, American University of Beirut, Beirut, Lebanon
b
School of Chemical and Biomolecular Engineering, The University of Sydney, Sydney, Australia

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

Article history: This paper presents a simulation flowsheet model of a waste tire pyrolysis process with feed capacity of
Received 24 August 2016 150 kg/h. A kinetic rate-based reaction model is formulated in a form implementable in the simulation
Revised 5 October 2016 package Aspen Plus, giving the flowsheet model the capability to predict more than 110 tire pyrolysis
Accepted 19 October 2016
products as reported in experiments by Laresgoiti et al. (2004) and Williams (2013) for the oil and gas
Available online xxxx
products respectively. The simulation model is successfully validated in two stages: firstly against exper-
imental data from Olazar et al. (2008) by comparing the mass fractions for the oil products (gas, liquids
Keywords:
(non-aromatics), aromatics, and tar) at temperatures of 425, 500, 550 and 610 °C, and secondly against
Waste tire
Pyrolysis
experimental results of main hydrocarbon products (C7 to C15) obtained by Laresgoiti et al. (2004) at tem-
Kinetics peratures of 400, 500, 600, and 700 °C. The model was then used to analyze the effect of pyrolysis process
Flowsheet model temperature and showed that increased temperatures led to chain fractions from C10 and higher to
Aspen Plus decrease while smaller chains increased; this is attributed to the extensive cracking of the larger hydro-
Net energy carbon chains at higher temperatures. The utility of the flowsheet model was highlighted through an
energy analysis that targeted power efficiency of the process determined through production profiles
of gasoline and diesel at various temperatures. This shows, through the summation of the net power gain
from the plant for gasoline plus diesel that the maximum net power lies at the lower temperatures cor-
responding to minimum production of gasoline and maximum production of diesel. This simulation
model can thus serve as a robust tool to respond to market conditions that dictate fuel demand and prices
while at the same time identifying optimum process conditions (e.g. temperature) driven by process
economics.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction (Torretta et al., 2015). However, such options can cause some seri-
ous environmental problems due to uncontrolled gaseous emis-
The potential of waste conversion to energy can be exploited to sions, VOCs, and dioxins. Proper disposal via advanced recycling
relieve the burden of energy supply from fossil fuels and ease envi- techniques such as pyrolysis is gaining pace since it re-
ronmental problems. In Europe and the US alone an estimated introduces the scrap tire into the process cycle and converts it into
4.6 million tons of rubber tires are disposed of annually (Roy gaseous and liquid products that can be used directly as fuel or
et al., 1995). These scrap tires are made up of a mixture of rubber, added to petroleum refinery feedstock (Dufton, 1987; Kawakami
steel cords, carbon black and other organic and inorganic com- et al., 1980; Roy et al., 1990).
pounds. Rubber, the major component, is a cross-linked Styrene- Very few studies investigated the modeling and simulation of
Butadiene polymer which is non-biodegradable; thus scrap tires waste tire pyrolysis. The complexity of cracking reactions and the
can reside in landfills for longer periods of time taking up valuable large spectrum of generated multiphase products render the math-
land space, and causing pollution and toxic fires. At the same time, ematical modeling of pyrolysis a tedious task. However, modeling
these waste materials represent a cheap and readily accessible pyrolysis may be facilitated by the abundance of literature studies
energy source. They can be used in incinerators for power genera- on the simulation of lignocellulose biomass pyrolysis and polymer
tion or they can be re-melted/re-molded into recreational products gasification. Many of these studies that investigated the pyrolysis
and gasification of biomass, coal, plastics, MSW, and tire feeds
⇑ Corresponding author. were simulated in Aspen PlusÒ using kinetic free equilibrium reac-
E-mail address: jz08@aub.edu.lb (J. Zeaiter). tion models (Visconti et al., 2014; Kannan et al., 2012; Zhu et al.,

http://dx.doi.org/10.1016/j.wasman.2016.10.024
0956-053X/Ó 2016 Elsevier Ltd. All rights reserved.

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Please cite this article in press as: Ismail, H.Y., et al. Pyrolysis of waste tires: A modeling and parameter estimation study using Aspen Plus . Waste Manage-
ment (2016), http://dx.doi.org/10.1016/j.wasman.2016.10.024
2 H.Y. Ismail et al. / Waste Management xxx (2016) xxx–xxx

2016). The main advantage of using thermodynamic equilibrium The paper is structured as follows: the technical background of
calculation is its independency of the flow pattern in the pyroly- tire pyrolysis is described first. This is then followed by a parame-
sis/gasification reactor. However, this can also be a disadvantage ter estimation study that identifies the kinetics of the pyrolysis
because the model is unspecific in its classification of the pyrolytic reactions. The flowsheet model is subsequently presented in detail
oil products, and cannot further relate to the design equations of followed by a discussion on the simulation product profiles and
the process. The main limiting assumption of such models is that energy results, before conclusions are presented.
residence time cannot be determined and reaction rates are irrele-
vant to reach thermodynamic equilibrium. Therefore, this 2. Tire pyrolysis conditions
approach impedes the ability to perform proper equipment design
calculations that are highly dependent on the kinetics of the Numerous literature studies have shown different operating
reactions. conditions for the pyrolysis of tires. As a result different trends
One possible solution to improve the accuracy of equilibrium- and results have been obtained. Table 1 summarizes the various
based models is to use experimental results to get the reaction operating conditions with the oil yield produced. As can be
parameters, but this makes the model very limited in its applica- observed, there are contradictory data in the literature on the
tion to a specific feed and to within a small range of experimental effects of temperature and pressure on the oil yield. For example,
operating conditions. Another approach is to develop quasi- (Williams and Brindle, 2003) observed that a temperature change
equilibrium temperature approach (Visconti et al., 2014), which from 300 °C to 720 °C, with a constant flow of nitrogen in a fixed
widens the applicability of the model, it however makes it less bed reactor, lead to an increase in the oil yields from 3% to 54.8%
accurate and unable to support the design equations with enough respectively. Similarly, Mastral et al. (2000) observed an increase
data. It should be noted that these approaches proved to be effec- in the yield from 36% at 400 °C up to 45% at 600 °C. Diez et al.
tive for gasification simulation but less so for pyrolysis simulation. (2004), Laresgoiti et al. (2004) also noted similar results with a
Alternatively, kinetic models are different from equilibrium 30% oil yield at 350 °C, 38% at 500 °C, increasing to 38% at 550 °C
models because they describe the conversion during the pyrolysis and 38.5% at 700 °C. However, Cunliffe and Williams (1998) and
reactions, which is crucial for designing the process, as well as Lee et al. (1998) both recorded a decrease in the oil yield from
assessing and studying its output at different operating conditions. 58.1% to 53.1%, and 48% to 30% with an increase in temperature
These rate models, unlike equilibrium models, are more accurate from 450 °C to 600 °C, and 700 °C to 900 °C, in a packed bed reac-
and detailed but are computationally rigorous, and complex. tor, and a fluidized bed reactor respectively. They attributed this to
Countless kinetic models can be found in the open literature on secondary reactions taking place at higher temperatures causing a
the pyrolysis of different feeds (e.g., Mazloom et al., 2009; decrease in the yields. To add to this contradiction, some studies
Sharma et al., 1998; Olazar et al., 2008), but the ability of simulat- reported the presence of a minimum/maximum oil yield in the
ing any of them remains a tedious challenge which, if completed, commonly studied temperature range. This, for example, was
would offer the ability to model accurately the pyrolysis processes. observed with Napoli et al. (1997) who used a glass tube reactor
Therefore, the need for developing a kinetic rate-based simula- swept with nitrogen gas, where the oil yield peaked at 450 °C with
tion capable of predicting with good accuracy the products of a lower yields at both 380 °C and 550 °C. Similar trends were
specific pyrolysis process under various operating conditions is of observed by Araki et al. (1979) and Tsai et al. (2007).
utmost necessity. It remains however a major challenge to develop In addition to the effect of temperature, other parameters play a
such a simulation because of the diverse and complex kinetics role in determining the efficiency of tire pyrolysis, namely, the
involved. heating rate and the type of catalyst used.
This paper develops a simulation model of a waste tire pyrolysis Williams and Brindle (2003) studied the effect of changing the
process under various operating conditions and validates the heating rate between 1 °C/min to 80 °C/min and found that the
developed model against data collected from open literature. maximum oil yield was observed at 15 °C/min. Other studies
Specifically, a kinetic rate-based model is incorporated to predict reported an overall maximum of 40% yield at a heating rate of
the evolution of more than 110 key tire pyrolysis products gener- 5 °C/min in the temperature range of 550–600 °C. Different
ated under various operating temperatures. The validated model is catalysts were studied in various investigations, each of which
used to carry out simulation analyses to understand fuel product reported a different effect. In most cases however, the catalyst
carbon chain distributions as well as their corresponding process increases the cracking of hydrocarbons into shorter chain lengths,
energy metrics. Finally the paper highlights the utility of such a effectively decreasing the liquids while increasing the amount of
process flowsheet model for operational market response. produced gas.

Table 1
Different operating conditions for pyrolysis.

Reference Reactor type T (°C) P (Pa) tm (min) Oil yield (%)

Araki et al. (1979) Fluidized Bed 350–500 101,325 12–20 42–38
Williams and Brindle (2003) Fixed Bed + fluidized catalyst bed 300–720 101,325 60 3.6–54.8
Roy et al. (1999) Fluidized bed, Vacuum 480–520 <10,000 n.a 10–60.7
Mirmiran et al. (1992) Multiple Hearth Furnace 200–500 <10,300 n.a 61
Lee et al. (1998) Fluidized bed 700–900 101,325 n.a 48–30
Tsai et al. (2007) Horizontally fixed bed 500 101,325 n.a Na
Napoli et al. (1997) Tubular furnace 380–550 101,325 Na 19
Mastral et al. (2000) Swept fixed bed 400–600 10
106 30 36–45
Kaminsky and Mennerich (2001) Fluidized bed >700 100,000 n.a 25–32
De Marco Rodriguez et al. (2001) Fluidized bed 300–700 101,325 30 4.8–38
Uçar et al. (2005) Fixed bed 550–800 101,325 60 67.4–72.2
Shah et al. (2007) Catalytic Batch reactor 300–400 n.a n.a 26–32
Zhang et al. (2008) Fixed bed 400–560 3500–4000 n.a 36.5–48.5
Rombaldo et al. (2008) Fixed bed 600–900 0.6–1 atm n.a 44–52
Dũng et al. (2009) Fixed Catalytic bed reactor 500 n.a 60 38–42

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Please cite this article in press as: Ismail, H.Y., et al. Pyrolysis of waste tires: A modeling and parameter estimation study using Aspen Plus . Waste Manage-
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 H.Y. Ismail et al. / Waste Management xxx (2016) xxx–xxx 3

3. Products from tire pyrolysis 4. Tire pyrolysis reaction kinetic model

Four main products are produced from waste tire pyrolysis, 4.1. Tire pyrolysis kinetic rate model
namely, solid char, gas, oil, and metals. The char can be used as a
low-grade carbon black, as a solid fuel, may be upgraded to acti- Pyrolysis reactions are decomposition reactions where large
vated carbon or it can be used as an energy source for the reactor. hydrocarbon chains that are mainly polyisoprene (natural rubber),
The gas, can also be used as an energy source for the process since polybutadiene and polystyrene-butadiene are decomposed (Quek
it has a high calorific value. The oil, which is the most important and Balasubramanian, 2012) into smaller chains ranging from C1
product, plays a vital role in the economic viability of the process to C24. These are classified into non-condensable gases C1-C4,
due to comprising commercially valuable chemicals such as ben- non-aromatics C5-C10, aromatics C5-C10, and tar (includes aromat-
zene, toluene, xylenes and limonene. Finally, metals that are a ics and non-aromatics) C11-C24.
mix of alloys are recycled and sold. In this current work, the simulation model illustrated in the
The main component in the gas product are butadiene, ethylene reaction network of Fig. 1 was based on the kinetics of Olazar
and methane. Other gases generated are C2-C5 alkanes and alkenes, et al. (2008) and as corrected by Niksiar et al. (2013). The compo-
as well as carbon monoxide and carbon dioxide. According to sition of the pyrolytic gas was based on the experimental results of
Williams and Brindle (2003), using Y-zeolite catalysts allowed Williams (2013), whereas the composition of the pyrolytic oil was
the increase of the alkane gases (C1-C4) while decreasing the alkene based on the experimental findings of Laresgoiti et al. (2004). In
gases. those works, the percentage of each component was reported at
The pyrolytic oil produced contains both short and long carbon given temperatures. This information was used to calculate the
chain molecules, as well as single and multiple ring structures. Its rate of formation of each product component and the kinetic rate
content has been analyzed throughout several studies, and accord- constants of each reaction. The feed to the Aspen PlusÒ model
ing to Roy et al. (1999), it is made of 87.3% carbon, 10.5% hydrogen, was defined as a non-conventional solid with elemental composi-
0.8% sulfur, 1.2% oxygen, and 0.2% nitrogen. Laresgoiti et al. (2004) tion based on that presented by Laresgoiti et al. (2004) and Islam
found a mixture of C6-C24 organic compounds, mainly composed of et al. (2013) ultanal and proxanal attributes respectively.
aromatics (53.4–74.8%), nitrogenated compounds (2.47–3.5%),
oxygenated compounds (2.29–4.85%) and some sulfur content 4.2. Kinetic parameter estimation
(1–1.4%). Aliphatic hydrocarbons and alkyl benzenes are the major
components of the oil, estimated to be C10 hydrocarbons. Distilla- A key feature of this paper is in retrofitting the kinetic rate
tion of the pyrolitic oil by Roy et al. (1999), gave 8% heavy naphtha, model (Eqs. (1)–(7)) by Olazar et al. (2008) and in estimating
16% kerosene, 24% light gas oil, 35% catalytic feed, and 17% bunker kinetic parameters suitable for flowsheet modeling in the Aspen
oil, while further distillation of the fraction below 204 °C was made PlusÒ simulation environment.
of 24.9% paraffins, 43.4% olefins, 6.6% naphthenes and 25.4% aro-
dX n
matics. Furthermore, it was found to contain alkanes (such as ¼ ðkg þ kl þ ka þ ki Þð1  X n Þ ð1Þ
dt
decane, undecane, dodecane, tridecane, octadecane, eicosane), aro-
matic compounds (such as benzene, toluene, ethylbenzene, xylene, dX g
styrene, naphthalene, phenanthrene and anthracene), ketones, ¼ kg ð1  X n Þ ð2Þ
dt
aldehydes, alkenes (such as propylene, butadiene, 1-pentene, iso-
prene, octene), phenols, alcohols, ethers and carboxylic acids. In dX l
addition to all of the aforementioned components, pyrolytic oil ¼ kl ð1  X n Þ ð3Þ
dt
was found to contain limonene as well. Higher temperatures lead
to a higher amount of polycyclic aromatic hydrocarbons, and it dX a
has been observed that around 30% of the oil has a boiling point
¼ ka ð1  X n Þ þ kia X i ð4Þ
dt
between 70 °C and 210 °C, which is the boiling point range speci-
fied for commercial petrol. Finally, Tsai et al. (2007) categorized dX t
¼ kit X i ð5Þ
the oil into four categories: light oil (C3-C8), diesel oil (C8-C18), fuel dt
(C18-C20) and residual oil (>C30).
Other than the carbon based components, some sulfur and dX c
¼ kic X i ð6Þ
nitrogen based compounds are also found in the pyrolyzed oil. dt
The majority of the sulfur is retained in the solid char, while some
sulfur compounds are found in the light naphtha fraction. As for dX i
¼ ki ð1  X n Þ  kia X i  kit X i  kic X i ð7Þ
the nitrogenous compounds, they are the following: aliphatic ami- dt
nes, amides and nitriles, pyridine and alkyl derivatives, aniline and where
their alkyl derivatives, quinolones and benzothiazoles. The ones X n = Overall mass conversion (kg converted/kg initial);
found to be most abundant however are the Pyridine and their X g ; X l ; X a ; X t ; X c ; X i = Mass fraction gas yield of gas, oil, aromatics,
alkyl derivatives. tar, char, and intermediates, respectively;
kg ; kl ; ka ; ki ; kia ; kit ; kic = Rate constants for tire-gas, tire-liquid,
tire-aromatic, tire-intermediate, intermediate-aromatic,
intermediate-tar, and intermediate-char kinetic respectively.

The reaction rate used in Aspen PlusÒ has to be in the specific

form presented in Eqs. (8)–(10).
r ¼ ½Kinetic factor½Driv ing force ð8Þ
 
E
½Kinetic factor ¼ A
Tn exp  ð9Þ
Fig. 1. Kinetic model for the pyrolysis of scrap tire by Olazar et al. (2008). RT
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4 H.Y. Ismail et al. / Waste Management xxx (2016) xxx–xxx

 
Mcomponent 39320
½Driv ing force ¼ mass fraction ¼ ð10Þ k2 ¼ 0:76  exp 
M total RT



In order to convert the model into the form accepted in Aspen 1:21  exp  39050  0:0409  exp  3730
Ò þ
RT
RT

Plus , the following steps and assumptions were applied: 1:21exp  39050
RT
þ 0:0885  exp  11320
RT
þ 0:195  exp  15920
RT
ð25Þ
1. The intermediate component terms, Xi, from Eqs. (1)–(7), were
eliminated by assuming pseudo-steady state conditions which


0:0885 exp  11320  0:0409 exp  3730
would help solve Eq. (7) as follows. k3 ¼
RT
RT

1:21 exp  39050
RT
þ 0:0885 exp  11320
RT
þ 0:195 exp  15920
RT

Solving for dX i
¼ 0, we get X i in terms of X n . ð26Þ
dt



ki 0:195 exp  15920  0:0409 exp  3730
Xi ¼ ð1  X n Þ ð11Þ k4 ¼
RT
RT

kia þ kit þ kic 1:21 exp  39050 þ 0:0885 exp  11320 þ 0:195 exp  15920
RT RT RT
2. Substituting the right-hand-side of Eq. (11) into Eqs. (1)–(6) ð27Þ
yields the new set of equations, 1
where A is in s and E in J/mol.
dX n
¼ ðkg þ kl þ ka þ ki Þð1  X n Þ ð12Þ 5. The ki0 s are fitted to the new equation form
dt

ki ¼ A
T n exp  RTE
where i = 1, 2, 3, and 4. For this purpose,
500 points were used from (Olazar et al., 2008) model to esti-
dX g mate the fit for k1, k2, k3, and k4 using Matlab’s curve fitting tool,
¼ kg ð1  X n Þ ð13Þ
dt which showed satisfactory fits for all ki0 s as illustrated in Fig. 2.
The following rate equations are obtained for the various sub-
dX l classes of products:
¼ kl ð1  X n Þ ð14Þ  
dt 23010
rg : C 1  C 4 ¼ 0:0283  exp  X 0n ðgasÞ ð28Þ
RT
 
dX a ki  
¼ ka þ kia ð1  X n Þ ð15Þ 1590
dt kia þ kit þ kic rl : C 5  C 10 ðnon-aromaticsÞ ¼ 0:014  exp   X 0n ðoilÞ
RT
ð29Þ
dX t ki  
¼ kit ð1  X n Þ ð16Þ 32890
dt kia þ kit þ kic ra : C 5  C 10 ðaromaticsÞ ¼ 0:5895  exp   X 0n ðoilÞ
RT
dX c ki ð30Þ
¼ kic ð1  X n Þ ð17Þ
dt kia þ kit þ kic
rt : C 11þ ðaromatics & non-aromaticsÞ
3. Substituting ð1  Xn Þ by X0n (the mass percentage tire remain-  
6300
ing) and lumping all kinetic rate constants in every equation ¼ 37:61:T 1:089  exp   X 0n ðoilÞ ð31Þ
RT
will transform Eqs. (12)–(17) into the following first order rate
expressions, 6. In the simulation model the feed is initially defined as non-
0
dX n conventional solid but for design purposes it is decomposed
¼ k1 X 0n ð18Þ
dt into its elemental components using a yield reactor, thus mass
conversion ‘‘X” has to be defined in terms of the elemental com-
dX g ponents. Hydrogen forms 7 wt% of the feed and it is the limiting
¼ kg X 0n ð19Þ
dt reactant so the mass conversion of H2 ‘‘XH2” can be best substi-
tuted for the mass conversion of tire feed ‘‘Xn” in (Olazar et al.,
dX l 2008)’s rate equations of the pyrolysis reactions. So the original
¼ kl X 0n ð20Þ
dt rate equation in terms of X0 n is divided by 0.07 and X0 n is
replaced by XH2.
dX a
¼ k2 X 0n ð21Þ 7. Thus the kinetic equations to be used in Aspen Plus model end
dt up being as follows:
 
dX t 23010
¼ k3 X 0n ð22Þ rg : C 1  C 4 ¼ 0:40428  exp  X H2 ðgasÞ ð32Þ
dt RT
 
dX c 1590
¼ k4 X 0n ð23Þ rl : C 5  C 10 ðnon-aromaticsÞ ¼ 0:2  exp   X H2 ðoilÞ
dt RT
4. The Arrhenius equation parameters, namely the pre- ð33Þ
exponential term, A, the activation energy, E, and the tempera-  
32890
ture coefficient n for k1 , k2 , k3 and k4 are estimated for ra : C 5  C 10 ðaromaticsÞ ¼ 8:4214  exp   X H2 ðoilÞ
temperatures of 200–700 °C based on the kinetic rates of RT
Eqs. (12)–(17),as follows:
   ð34Þ
23010 1590
k1 ¼ 0:0283  exp  þ 0:014  exp 
RT RT rt : C 11þ ðaromatics & non-aromaticsÞ
     
39320 3730 6300
þ 0:76  exp  þ 0:0409  exp  ð24Þ ¼ 537:28  T 1:089  exp   X H2 ðoilÞ ð35Þ
RT RT RT
Ò
Please cite this article in press as: Ismail, H.Y., et al. Pyrolysis of waste tires: A modeling and parameter estimation study using Aspen Plus . Waste Manage-
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 H.Y. Ismail et al. / Waste Management xxx (2016) xxx–xxx 5

Fig. 2. Results for the fitting of k1, k2, k3, and k4 respectively to the Arrhenius form.

The individual rate expressions for every product can now be The feed was set at 150 kg/h with a size distribution (SD) of the
deduced from these general expressions by multiplying them feed tires 1.1–1.9 m. It was defined as a non-conventional solid
(Eqs. (32)–(35)) by the estimated individual component fraction with the following Proxanal and Ultanal (Laresgoiti et al., 2004;
in the gas and oil products. This information (concerning the indi- Quek and Balasubramanian, 2012) attributes (Table 2).
vidual component fraction) was obtained from a literature experi-
mental data Williams (2013) and Laresgoiti et al. (2004) where the 5.2. Flow Sheet model
percentage of every chemical component in the produced gas and
oil were given under a wide range of temperatures (i.e. 300– Scrap tires are firstly fed into a shredder where the particle size
700 °C). This lead to estimating the rate expression for 116 differ- is reduced to less than 1.5 cm in size (Fig. 3). In the corresponding
ent products as presented in the Appendix. It should be noted that Aspen Plus flow sheet of Fig. 4, the shredder (SHREDER) is the first
the data in the Appendix presents the pre-exponential term, the unit, where about 24 kW/h of work is consumed for shredding
activation energy, and the temperature dependence (according to 150 kg/h of tires.
Eq. (9)) of the first order reaction that produces the desired product The shredded tires are then introduced to a fixed bed reactor,
while maintaining hydrogen as the limiting reactant. These equa- where the pyrolysis reactions take place to form char, gas, and
tions follow the form presented in Eq. (36). oil compounds. In the Aspen Plus flowsheet the pyrolysis reaction
  stage is modelled as a combination of a yield reactor (DECOMPOS),
E
r i ¼ A  Tn  exp   X H2 ð36Þ a plug flow reactor (PFR1) and a furnace. The yield reactor
RT (DECOMPOS) that is predefined in Aspen Plus Library converts
the nonconventional solid feed particles into its conventional ele-
where ri is the individual rate equation for each product E in (kJ/-
mental component, this reactor is operated in the range of 300–
mol) and A in s1.
700 °C under 1 atm. Then, in the Plug Flow Reactor (PFR1), of
0.15 m diameter and 1.7 m length, the pyrolysis reactions were
Ò
5. Tire pyrolysis flow sheet model in Aspen Plus simulated for temperatures ranging from 300 °C to 700 °C to pro-
duce oil and gas products according to the previously defined
5.1. The feed and corresponding setup of the reaction model kinetics in the Appendix.

The reactions that take place are decompositions of large hydro-

Table 2
carbon chains into smaller molecules. In Aspen Plus the feed is Proxanal and Ultanal elemental analysis of the waste tire feed.
defined by its elemental components and not by its chemical com-
Element Wt% Wt%
position. As a result, the reactions are a combination of elemental
components giving desired products. C 75 Ash 13.5
H 7 Moisture 1.5
General Reaction form:
N 0.3 Fixed carbon 30
Cl 0 Volatile material 55
nC þ mH2 þ pO2 þ kN2 þ gS þ rCl2 ! Cn H2m O2p N2k Sg Cl2r
S 1.5
O 2.7
With the products being Gas, Oil, Carbon black (char), and Metal.
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Please cite this article in press as: Ismail, H.Y., et al. Pyrolysis of waste tires: A modeling and parameter estimation study using Aspen Plus . Waste Manage-
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6 H.Y. Ismail et al. / Waste Management xxx (2016) xxx–xxx

Fig. 3. Process flow diagram for waste tire pyrolysis process.

The products exiting the reactors are in vapor phase at temper- products formed (Table 3). Simulation results were validated
atures between 300 and 700 °C except carbon black and metal ash; against literature values given by Niksiar et al. (2013).
these non-vapor components are separated from the vapor compo- The above table demonstrates the product formation (in kg/h)
nents in a separator (Vessel 1). Char is further separated from the at temperatures of 400, 500, 600 and 700 °C with a continuous feed
solid metals using a separator unit (HYCYC1). The vapor stream of 150 kg/h. It is clear that as the temperature increase char
product is cooled down from 300–700 °C to 30 °C using cooling decrease while the gas and oil products increase. This is in line
water in a heat exchanger (HEX1). The stream is further separated with experimental data obtained by Niksiar et al. (2013) who
to a liquid phase containing oil products and a vapor phase con- observed a similar behavior at temperatures in the range of 425–
taining non- condensable gas products using a separator (Vessel 610 °C. This is mainly due to the fact that at higher temperatures
2). Thirty percent of the char products are burned in a furnace to a higher rate of cracking takes place thus larger carbon chains
produce the required energy for heating the reactor, the furnace are broken into smaller chains leaving less carbon residues.
corresponds to the Gibbs Reactor unit (FURNACE) that is a build-
in reactor in Aspen Library as shown in Fig. 4.
6.2. Comparing simulation and experimental results

6. Results and discussion The oil products obtained from the current simulations were
classified between C7-C15, and the predicted weight fraction of
6.1. Simulation results each individual product were validated against experimental mea-
surements (as reported by Laresgoiti et al. (2004)) at the various
The effect of temperature was analyzed by running the simula- temperatures of 400, 500, 600 and 700 °C as shown in Fig. 5. It is
tion at different temperatures and recording the amounts of clear that the simulation results predict the experimental data
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ment (2016), http://dx.doi.org/10.1016/j.wasman.2016.10.024
 H.Y. Ismail et al. / Waste Management xxx (2016) xxx–xxx 7

Fig. 4. A snapshot of the Aspen Plus simulation flowsheet for the waste tire pyrolysis process.

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Please cite this article in press as: Ismail, H.Y., et al. Pyrolysis of waste tires: A modeling and parameter estimation study using Aspen Plus . Waste Manage-
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8 H.Y. Ismail et al. / Waste Management xxx (2016) xxx–xxx

Table 3
Simulation results for tire pyrolysis products at different temperatures with a feed of 150 kg/h.

Temperature (°C) Char (kg/h) Metal (kg/h) Gas (kg/h) Oil (kg/h)
400 27.24 20.2 1.63 97.2
500 26.6 20.2 2.55 97.2
600 25.6 20.2 3.5 97.6
700 24.2 20.2 4.4 98.26

Fig. 5. Simulated and experimental results for C7-C15 weight fractions of the oil and gas products at temperatures of 400, 500, 600 and 700 °C (Laresgoiti et al., 2004).

with a reasonable accuracy where the average relative error was was different from the results of the conical spouted reactor of
found to be within ±24.61% at 400 °C, ±17.95% at 500 °C, ±9.93% Olazar et al. (2008). From the simulation results it is obvious that
at 600 °C, ±9.09% at 700 °C. This discrepancy between the experi- at higher temperatures the big hydrocarbon chains C10-C15 decom-
mental and simulation results could be attributed to the fact that pose to smaller ones <C10. The mismatch between the model and
the experiments of Laresgoiti et al. (2004) were conducted at dif- data is also due to the fact that (Laresgoiti et al., 2004) had the aro-
ferent heating rates than those at which the model of Olazar matic compounds and liquids (C7-C9) at slightly higher rates
et al. (2008) was developed and with a different feed composition. whereas the tar components were lower than (Olazar et al.,
Also some of this discrepancy can be attributed to the different 2008). This caused the model to overpredict at C10+ and underpre-
reactor types employed in the previous two studies. dict at C9.
Fig. 5 shows that the biggest fraction of the products is concen- In general this modeling approach proves to be suitable in pre-
trated between C7-C15 hydrocarbon chains. This constitutes nearly dicting the product distribution over a wide range of operating
90% of all the gas and oil products. The C10 products alone form temperatures (400–700 °C) with very good accuracy.
around 35% of the products. Fig. 6 presents a direct comparison between the experimental
It can be also depicted from Fig. 5 that the error is decreasing as data from Olazar et al. (2008) and the simulated results for the
the temperature increases to 700 °C, this indicates that (Laresgoiti gas, aromatics, and liquid (non-aromatic) products obtained at
et al., 2004)’s data starts to follow the suggested mathematical temperatures of 425, 500, 550, and 610 °C. As the temperature
model at higher temperatures. However as the temperature increase the liquid and tar products decrease while the aromatic
increases the error difference of the C10 components seems to and gas products increase. This behavior is consistent with the
widen while it decreases for all other carbon chains. This is best experimental literature data, and it is mainly due to the cracking
attributed to the fact that in Laresgoiti et al. (2004) the aromatics of big chains (tar) into smaller ones, and the reformation of the
fraction were inconsistent in behavior against temperature smaller chains (liquid) to their corresponding aromatic structure
changes in the unstirred autoclave (i.e. aromatics were increasing because more energy is available for this reforming at higher
or decreasing with an increase of temperature). This behavior temperatures. It is very clear that the simulated data fits the
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Please cite this article in press as: Ismail, H.Y., et al. Pyrolysis of waste tires: A modeling and parameter estimation study using Aspen Plus . Waste Manage-
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 H.Y. Ismail et al. / Waste Management xxx (2016) xxx–xxx 9

0.4
Gas Simulation
0.35
Liquid
Simulation
0.3

Mass Yield Fraction

Aromatic
Simulation
0.25
Tar Simulation
0.2
Gas
Experimental
0.15
Liquid
Experimental
0.1
Aromatic
0.05 Experimental
Tar
0 Experimental
400 450 500 550 600 650
Temperaure (C)

Fig. 6. The experimental (Niksiar et al., 2013) and simulated product yields at temperatures of 425, 500, 550, and 610 °C.

experimental measurements with high accuracy of ±2%, which combustion power produced. Since gasoline combustion power
clearly demonstrates the effectiveness of the parameters retrofit- produced increases at a higher rate than the increase in the power
ting approach and the validity of the simulation. consumed by the plant, the net power produced increases with
temperature.
6.3. Energy analysis The net power produced is calculated according to the following
equation:
In order to determine the efficiency of the process an energy
NP ¼ A  B  C  D
analysis was conducted at a temperature range of 300–700 °C,
for the major oil products Gasoline and Diesel. The Gasoline where
includes hydrocarbon components from C4-C10 and Diesel includes NP is the net power produced from the plant for a given oil pro-
hydrocarbon components from C11 to C21. duct at a given temperature,
By subtracting the heat of combustion of the oil products from A is the combustion power produced from a given oil product at
the power consumption that includes (reactor body heating, mate- a given temperature,
rial feed heating, activation energy needed for the pyrolysis reac- B is the power consumed for heating the feed for the desired
tions, and the electrical power consumed by the shredder) the temperature and the pyrolysis activation energy needed for
net power gain from the plant is obtained for gasoline, and diesel the reactions,
at each given temperature as illustrated in Fig. 7. C is the power consumed for heating the reactor body at the
At each operating temperature the pyrolysis products have dif- desired temperature, and
ferent compositions (Fig. 5). As a reflection of this change the D is the electrical power required in the shredder.
power gain of the plant also changes (Fig. 7). As the temperature
increases there is more decomposition of larger hydrocarbon To compare the normalized power production for the two oil
chains from C10 and higher that is obvious in Fig. 5, this corre- products (gasoline, and diesel), NP, A, B, C, and D where normalized
sponds to the decrease of the diesel combustion power produced, and plotted (Fig. 8) at temperatures of 400 and 600 °C for the two
since diesel is composed of larger hydrocarbon chains. While gaso- oil products. This shows the contribution of each oil product
line that is of lower hydrocarbon chains increases in composition towards the net power production at each temperature. Referring
as the temperature increases, corresponding to an increase in to Fig. 7, the production seems at the first glance to be in favor

800

700

600
Power (KW)

500

400

300

200
300 350 400 450 500 550 600 650 700
Temperature (C)
C4-C10 Net Power Produced C4-C10 Combustion Power Produced
C11-C21 Net Power Produced C11-C21 Combustion Power Produced

Fig. 7. The net and combustion power produced by the pyrolysis products for gasoline, and diesel for an operating temperature range of 300–700 °C. Lines indicate trends
only.
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Please cite this article in press as: Ismail, H.Y., et al. Pyrolysis of waste tires: A modeling and parameter estimation study using Aspen Plus . Waste Manage-
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10 H.Y. Ismail et al. / Waste Management xxx (2016) xxx–xxx

Fig. 8. Normalized powers produced and consumed for gasoline (dark-coloured portion of bar) and diesel (light-coloured portion of bar) at temperatures 400 °C (left) and
600 °C (right).

of operating at the lower temperatures, since the summation of the the lower mass fractions of C10-C15 and higher mass fractions for
net power produced for gasoline and diesel is higher at lower tem- C7-C9. Moreover, the increase in temperature favored the produc-
peratures with the maximum production of diesel and the mini- tion of more aromatics and less tar and non-aromatics. This was
mum production of gasoline found at 300 °C (Fig. 7). However, attributed to the decomposition of tar (long chains) into smaller
Fig. 8 highlights the influence of market supply and demand for chains and the reformation of the small chains to their correspond-
the petrol products; fuel price fluctuations over time will play a ing aromatic form.
crucial role in the decision to increase the production ratio of diesel Furthermore, operating at low temperatures was determined to
to gasoline. As such, market drivers present an economic optimiza- be the most energy efficient from a net energy point of view, where
tion that determines the optimal operating temperature for tire diesel is produced at the maximum and gasoline at the minimum
pyrolysis. amounts. However, since the market demand for diesel, and gaso-
line changes with time, along with their respective price fluctua-
7. Conclusions tions, operating at lower temperatures may not be the most
economically feasible point. The simulation model presented in
This paper provides a model-based analysis of waste tire pyrol- this paper offers itself as a tool that will allow the pyrolysis plant
ysis. A flowsheet simulation was developed to predict the pyrolysis operator to respond economically to market changes by targeting
process products under different operating conditions. It was vali- most economical operating temperatures.
dated against experimental data obtained by Olazar et al. (2008)
and Laresgoiti et al. (2004). The simulation model proved to predict Acknowledgments
the hydrocarbon product mass fractions with high accuracy. As the
process temperature increased, the larger hydrocarbon chains The financial support of the American University of Beirut
were decomposed into smaller ones, and this was obvious with through its University Research Board (URB) is greatly
acknowledged.

Appendix A

Tire pyrolysis reactions with their corresponding estimates of their reaction constants used for modeling tire pyrolysis process in Aspen
Plus.

No Reaction Product A (s1) E (kJ/mol) n (Temperature

coefficient)
1 C þ 2H2 ! CH4 Methane 4.877 23.01 0
2 2C þ 3H2 ! C2 H6 Ethane 0.520 23.01 0
3 2C þ 2H2 ! C2 H4 Ethene 2.386 23.01 0
4 3C þ 4H2 ! C3 H8 Propane 0.277 23.01 0
5 3C þ 3H2 ! C3 H6 Propene 0.446 23.01 0
6 4C þ 5H2 ! C4 H10 Butane 0.122 23.01 0
7 4C þ 4H2 ! C4 H8 Butene 0.144 23.01 0
8 4C þ 3H2 ! C4 H6 Butalyne 0.981 23.01 0
9 C þ O2 ! CO2 Carbon Dioxide 0.226 23.01 0
10 C þ 12 O2 ! CO Carbon Monoxide 0.096 23.01 0
11 H2 þ S ! H2 S Hydrogen Sulfide Equilibrium Equilibrium 0
12 5C þ 6H2 ! C5 H12 Pentane 0.339 23.01 0
13 5C þ 4H2 ! C5 H8 Pentalyne 0.066 23.01 0

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 H.Y. Ismail et al. / Waste Management xxx (2016) xxx–xxx 11

Appendix A (continued)
No Reaction Product A (s1) E (kJ/mol) n (Temperature
coefficient)
14,15 6C þ 6H2 ! C6 H12 Methylcyclopentene 0.009, 0.009 1.59 0
16 8C þ 7H2 ! C8 H14 Methylhexadiene 0.016 1.59 0
17,19 8C þ 9H2 ! C8 H18 Trimethylpentane 0.023, 0.019 1.59 0
18 7C þ 7H2 ! C7 H14 Dimethylcyclopentane 0.015 1.59 0
20 8C þ 9H2 ! C8 H18 Dimethylhexane 0.044 1.59 0
21 7C þ 7H2 ! C7 H14 Ethylcyclopentane 0.008 1.59 0
22 7C þ 7H2 ! C7 H14 Methylcyclohexene 0.045 1.59 0
23 8C þ 8H2 ! C8 H16 Dimethylcyclohexane 0.010 1.59 0
24 8C þ 8H2 ! C8 H16 Octene 0.007 1.59 0
25 8C þ 7H2 ! C8 H14 Dimethylhexadiene 0.011 1.59 0
26, 27 8C þ 8H2 ! C8 H16 Ethylcyclohexane 0.054, 0.007 1.59 0
28 9C þ 9H2 ! C9 H18 Trimethylcyclohexane 0.003 1.59 0
29 9C þ 9H2 ! C9 H18 Nonene 0.017 1.59 0
30 9C þ 9H2 ! C9 H18 Methylocatene 0.164 1.59 0
31 10C þ 8H2 ! C10 H16 Dlimonene 0.035 1.59 0
32 10C þ 8H2 ! C10 H16 Pinene 0.064 1.59 0
33 10C þ 8H2 ! C10 H16 Limonene 0.619 1.59 0
34 6C þ 3H2 ! C6 H6 Benzene 1.654 33.89 0
35 7C þ 4H2 ! C7 H8 Toluene 7.305 33.89 0
36 8C þ 5H2 ! C8 H10 Ethylbenzene 4.708 33.89 0
37 8C þ 5H2 ! C8 H10 Xylene 4.476 33.89 0
38 8C þ 4H2 ! C8 H8 Styrenetyrene 4.049 33.89 0
39 8C þ 5H2 ! C8 H10 Dimethylbenzene 1.084 33.89 0
40 9C þ 6H2 ! C9 H12 Cumene 1.070 33.89 0
41 9C þ 5H2 ! C9 H10 Ethylmethylbenzene 0.5 33.89 0
42 9C þ 6H2 ! C9 H12 Propylbenzene 1.117 33.89 0
43, 44 9C þ 6H2 ! C9 H12 Ethylbenzene 1.189, 2.128 33.89 0
45 9C þ 6H2 ! C9 H12 Trimethylbenzene 0.424 33.89 0
46 6C þ 3H2 þ O ! C6 H6 O Phenol 0.497 33.89 0
47, 51, 52 9C þ 5H2 ! C9 H10 Methylethenylbenzene 1.532, 0.634, 0.344 33.89 0
48 7C þ 2:5H2 þ N ! C7 H5 N Benzonitrile 0.528 33.89 0
49 9C þ 5H2 ! C9 H10 Propenylbenzene 0.567 33.89 0
50 9C þ 6H2 ! C9 H12 C3-benzene 1.808 33.89 0
53 10C þ 7H2 ! C10 H14 Isopropyltoluene 3.850 33.89 0
54 9C þ 6H2 ! C9 H12 C3-benzene 0.392 33.89 0
55 9C þ 5H2 ! C9 H10 Dihydro-1H-indene 0.922 33.89 0
56 9C þ 4H2 ! C9 H8 1H-indene 1.278 33.89 0
57 10C þ 7H2 ! C10 H14 Butylbenzene 1.058 33.89 0
58 10C þ 7H2 ! C10 H14 Ethyldimethylbenzene 0.338 33.89 0
59,61 10C þ 7H2 ! C10 H14 Isopropylmethylbenzene 0.769, 0.678 33.89 0
60 10C þ 7H2 ! C10 H14 Ethyldimethylbenzene 0.397 33.89 0
62, 7, 9, 73 9C þ 5H2 ! C9 H10 Dihydromethyl-1H-indene 0.516, 0.759, 3.694, 0.433 33.89 0
63 10C þ 7H2 ! C10 H14 Tetramethylbenzene 0.383 33.89 0
64 10C þ 7H2 ! C10 H14 Tetramethylbenzene 0.4 33.89 0
65 10C þ 7H2 ! C10 H14 Ethylisopropylbenzene 0.198 33.89 0
66 8C þ 5H2 þ 0:5O2 ! C8 H10 O Dimethylphenol 0.316 33.89 0
68 7C þ 3H2 þ O2 ! C7 H6 O2 Benzoic acid 0.549 33.89 0
70 10C þ 5H2 ! C10 H10 Methyl-1H-indene 0.539 33.89 0
71 10C þ 6H2 ! C10 H12 Tetrahydronaphalene 0.562 33.89 0
72 10C þ 7H2 ! C10 H14 C4-benzene 0.165 33.89 0
74 10C þ 4H2 ! C10 H8 Naphthalene 0.979 33.89 0
75 10C þ 7H2 þ 0:5O2 ! C10 H14 O Isopropylphenol 0.056 33.89 0
76 7C þ 2:5H2 þ 0:5N2 þ Benzothiazole 1.2 33.89 0
2S ! C7 H5 NS2
77 12C þ 8H2 ! C12 H16 Tetrahydroethylnaphthalene 47.264 6.3 1.089
78 12C þ 9H2 ! C12 H18 C6-benzene 47.815 6.3 1.089
79,80 11C þ 5H2 ! C11 H10 Methylnaphthalene 125.001, 156.807 6.3 1.089
81, 2 12C þ 7H2 ! C12 H14 Trimethylindene 9.307, 95.891 6.3 1.089
83 12C þ 5H2 ! C12 H10 Diphenyl 142.201 6.3 1.089
84, 5 12C þ 6H2 ! C12 H12 Ethylnaphthalene 97.289, 37.367 6.3 1.089

(continued on next page)

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Please cite this article in press as: Ismail, H.Y., et al. Pyrolysis of waste tires: A modeling and parameter estimation study using Aspen Plus . Waste Manage-
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12 H.Y. Ismail et al. / Waste Management xxx (2016) xxx–xxx

Appendix A (continued)
No Reaction Product A (s1) E (kJ/mol) n (Temperature
coefficient)
86, 7, 8 12C þ 6H2 ! C12 H12 Dimethylnaphthalene 85.169, 83.486, 119.843 6.3 1.089
89 10C þ 4:5H2 þ 0:5N2 ! C10 H9 N Ethylquinoline 184.356 6.3 1.089
90 14C þ 14H2 ! C14 H28 n-C14 118.294 6.3 1.089
91 12C þ 5H2 ! C12 H10 Acenaphthene 36.147 6.3 1.089
92 15C þ 16H2 ! C15 H32 n-C15 56.974 6.3 1.089
93, 4, 5 15C þ 9H2 ! C15 H18 Trimethylnaphthalene 88.852, 31.429, 29.175 6.3 1.089
96 13C þ 5H2 ! C13 H10 Fluorene 47.770 6.3 1.089
97, 8 15C þ 8H2 ! C15 H16 Dimethyldiphenyl 60.554, 11.521 6.3 1.089
99 15C þ 15H2 ! C15 H30 Pentadecene 17.880 6.3 1.089
100 16C þ 17H2 ! C16 H34 n-C16 46.822 6.3 1.089
101 14C þ 5H2 ! C14 H10 Phenanthrene 34.666 6.3 1.089
102 14C þ 5H2 ! C14 H10 Anthracene 38.059 6.3 1.089
103 15C þ 6H2 ! C15 H12 Methylphenanthrene 36.925 6.3 1.089
104 15C þ 15H2 þ O2 ! C15 H30 O2 Pentadecanoic acid 64.017 6.3 1.089
105, 6, 7 15C þ 6H2 ! C15 H12 Methylphenanthrene 41.028, 46.908, 82.056 6.3 1.089
108 19C þ 20H2 ! C19 H40 n-C19 12.247 6.3 1.089
109 19C þ 8H2 ! C19 H16 Trimethylphenanthrene 22.599 6.3 1.089
110 19C þ 19H2 ! C19 H38 Isopropylmethylphenanthrene 51.627 6.3 1.089
111 20C þ 21H2 ! C20 H42 n-C20 13.594 6.3 1.089
112 21C þ 22H2 ! C21 H44 n-C21 15.524 6.3 1.089
113 22C þ 23H2 ! C22 H46 n-C22 12.028 6.3 1.089
114 23C þ 24H2 ! C23 H48 n-C23 15.641 6.3 1.089
115 24C þ 25H2 ! C24 H50 n-C24 3.029 6.3 1.089
116 11C þ 12H2 ! C11 H24 n-C11 35.684 6.3 1.089

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