Rudy, A., et al.

, Simulation of the Hydrodealkylation of Toluene Using Conversion Reactor, Keluwih: Jurnal Sains dan
Teknologi, Vol.5(1), 19-26, Februari 2024.
https://doi.org/10.24123/saintek.v5i1.6351

Original Research

Simulation of the Hydrodealkylation of Toluene

Using Conversion Reactor
Rudy Agustriyanto 1*, Puguh Setyopratomo 1, Endang Srihari Mochni 1, Eddy Purwanto 1
1
Jurusan Teknik Kimia, Fakultas Teknik, Universitas Surabaya, Surabaya-Indonesia
* corresponding author: [email protected]

Abstract—The hydrodealkylation of toluene is frequently used to produce the more valuable compound benzene. This process is
widely employed in the petrochemical industry. Through hydrodealkylation, toluene undergoes a transformation, resulting in the
production of valuable chemicals such as benzene and diphenyl. The objective of this study is to present the results obtained from
simulating the process of toluene dealkylation using Aspen HYSYS. The feed to the reactor must contain toluene and hydrogen, while
the recommended operating conditions are at 500 oC to 650 oC and 20 to 40 atm pressure to achieve 90% conversion. For this purpose,
a conversion reactor has been selected as the preferred type. The simulation outcomes are particularly valuable during the initial
stages of designing a production facility for benzene. The mass and energy balance calculations can be easily performed using Aspen
HYSYS. Future research may focus on investigating different reactor types while considering the kinetics of the reaction.

Keywords: aspen HYSYS, hydrodealkylation, simulation, toluene

Abstrak—Hidrodealkilasi toluena sering digunakan untuk menghasilkan senyawa yang lebih bernilai yaitu benzene. Proses ini
banyak digunakan dalam industri petrokimia. Melalui hidrodealkilasi, toluena mengalami transformasi, menghasilkan bahan kimia
berharga seperti benzene dan diphenyl. Tujuan dari penelitian ini adalah untuk menyajikan hasil yang diperoleh dari mensimulasikan
proses dealkilasi toluena menggunakan Aspen HYSYS. Umpan ke reaktor harus mengandung toluena dan hidrogen, sedangkan
kondisi operasi yang direkomendasikan adalah pada suhu 500 oC hingga 650 oC dan tekanan 20 hingga 40 atm untuk mencapai
konversi 90%. Untuk tujuan ini, reaktor konversi telah dipilih sebagai tipe yang disukai. Hasil simulasi sangat berharga selama tahap
awal perancangan fasilitas produksi benzene. Perhitungan neraca massa dan energi dapat dengan mudah dilakukan menggunakan
Aspen HYSYS. Penelitian masa depan dapat fokus pada penyelidikan berbagai jenis reaktor sambil mempertimbangkan kinetika
reaksi.

Kata kunci: aspen HYSYS, hidrodealkilasi, simulasi, toluene

INTRODUCTION
Benzene, toluene, ethyl benzene, and xylene (BTEX) originate from crude oil and can be
found near natural gas and petroleum reserves (Bustillo-Lecompte et al., 2018).
Toluene is an organic compound that belongs to the group of aromatic hydrocarbons. It
has a chemical formula of C7H8 and can be found in crude oil as well as some fossil fuel products.
Toluene has good solvent properties and is widely used in the industry as a solvent, raw material
in paint production, organic chemical, and also as a raw material in the production of explosives
such as trinitrotoluene (TNT) (Atsdr, 2017; PubChem, n.d.).
Benzene is also an organic compound that belongs to the group of aromatic
hydrocarbons with the chemical formula C6H6 (Trans Pacific Petrochemical Indotama, n.d.). This
compound has a hexagonal ring structure consisting of carbon and hydrogen atoms. Benzene is
a colorless compound that readily evaporates and has a distinct aroma. Benzene is used in
various industries, including petrochemical, pharmaceutical, plastics, and solvents. However,
benzene is also known to be a hazardous substance to humans. Long-term exposure to benzene
can be associated with serious health risks, including the risk of developing blood cancer such as
leukemia (Barton, 2023) (PubChem, n.d.). Benzene itself has been limited to less than 1% in
gasoline due to its known carcinogenic properties in humans. Its non-industrial applications have
also been restricted for the same reasons (Trans Pacific Petrochemical Indotama, n.d.).
Toluene hydrodealkylation into benzene is an important petrochemical process that
represents the largest end use in the US and West Europe (Meidanshahi et al., 2011; Iranshahi
et al., 2017) as well as in East Europe (Iranshahi et al., 2017). Because benzene is more valuable
than toluene, the majority of the produced toluene is converted to benzene through

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Rudy, A., et al., Simulation of the Hydrodealkylation of Toluene Using Conversion Reactor, Keluwih: Jurnal Sains dan
Teknologi, Vol.5(1), 19-26, Februari 2024.
https://doi.org/10.24123/saintek.v5i1.6351

hydrodealkylation (Meidanshahi et al., 2011). This reaction is also known as toluene

disproportionation.
Recent studies on the hydrodealkylation of toluene include the kinetic and
thermodynamic analysis of this reaction under actual industrial operating conditions (Ali et al.,
2022). Another study attempts to integrate stochastic programming and reliability in the optimal
synthesis for this reaction (Chen et al., 2022). Furthermore, Liu (Liu et al., 2015) proposed a new
double flash process and heat integration for improved energy utilization. Studies on various
catalysts have also been conducted for the hydrodealkylation of toluene, resulting in different
side products (varying composition of the resulting products) (Mesa et al., 2019) (Albahar et al.,
2020).
Lian (Lian et al., 2023) also conducted a study on benzene production from different
routes, specifically the methane dehydroaromatization reaction.
The complete hydrodealkylation process of toluene encompasses 9 distinct unit
operations, including a reactor, recycle compressor, furnace, 2 heat exchangers, vapor-liquid
separator, and 3 distillation columns. The typical feedstocks for this process are hydrogen and
toluene. The primary output of this process is benzene, accompanied by the secondary products
of methane and biphenyl. (Iranshahi et al., 2017) (Douglas, 1988). This process can be conducted
with or without the presence of catalysts. The catalytic process relies on the utilization of
catalysts like nickel or clinoptilolite to facilitate the hydrogenation reaction.
In this process, toluene undergoes hydrodealkylation within a uniform and gaseous non-catalytic
medium, resulting in the production of benzene and methane as primary products. Additionally,
through an equilibrium reaction, benzene can lose hydrogen and transform into diphenyl. The
main product obtained is benzene, while hydrogen and diphenyl (biphenyl) are generated as by-
products. The reactions and their corresponding rate laws are provided below (Douglas, 1988;
Luyben et al., 1999):

1. C7 H8 H 2  C6 H6  CH4 H  50 kJ / mole

(Toluene Hydrogen  Benzene  Methane)

R1  1.9580 108 e( 25616 / T ) pT pH

1/ 2

2. 2C6 H6 C12 H10  H 2 H  0kJ / mole

(2 Benzene BiPhenyl  Hydrogen)

R2  1.2115106 e( 25616 / T ) pB  5.1662106 e( 25616 / T ) pD pH

2

The aim of this paper is to conduct a steady state simulation for the toluene
hydrodealkylation process using Aspen HYSIS. This is a preliminary study to enhance the
utilization of HYSYS in order to conduct more advanced research.
Our paper focuses on the steady-state simulation of the toluene hydrodealkylation
process using Aspen HYSYS. While there exist numerous studies and papers on simulation using
HYSYS for various chemical reaction systems, our work delves into a specific reaction pathway
that has significant industrial relevance due to the economic importance of benzene production
from toluene.
The application of Aspen HYSYS for simulating the hydrodealkylation process holds
immense significance in the petrochemical industry, where the conversion of toluene to
benzene is a fundamental operation. By showcasing the utilization of HYSYS for this particular
reaction, we contribute to the advancement of simulation techniques in a crucial industrial
sector.

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Rudy, A., et al., Simulation of the Hydrodealkylation of Toluene Using Conversion Reactor, Keluwih: Jurnal Sains dan
Teknologi, Vol.5(1), 19-26, Februari 2024.
https://doi.org/10.24123/saintek.v5i1.6351

Our study incorporates key process parameters such as temperature, pressure, and
reactor type, offering insights into optimizing the hydrodealkylation process for efficient
benzene production. This integration of process parameters within the Aspen HYSYS framework
adds value to our research by providing practical guidance for process engineers and
researchers.
While our paper serves as a preliminary study, it lays the groundwork for more advanced
research in the field of chemical process simulation. The utilization of Aspen HYSYS opens
avenues for further investigations into reaction kinetics, catalyst selection, and process
optimization, which are integral to enhancing the efficiency and sustainability of industrial
processes.

METHOD
The Aspen HYSYS software would be used to simulate this process (toluene
hydrodealkylation). All materials involved in the reaction are already available in the HYSYS
component list. SRK were selected as the thermodynamic model (fluid package). The simulation
procedure is as follows:
 Start
 Determining the involved components.
 Selecting SRK as the thermodynamic model.
 Creating a process flowsheet.
 Completing equipment specifications and operating conditions.
 Process simulation
 Evaluation
 End

The process diagram is shown in Fig.1, meanwhile, the feed composition to the process
is indicated in Table 1.

Fig. 1. Toluene hydrodealkylation process

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Rudy, A., et al., Simulation of the Hydrodealkylation of Toluene Using Conversion Reactor, Keluwih: Jurnal Sains dan
Teknologi, Vol.5(1), 19-26, Februari 2024.
https://doi.org/10.24123/saintek.v5i1.6351

Table 1
Feed Composition

Component Feed (lbmole/h) Recycle Gas Recycle

(lbmole/hr) (lbmole/hr)
H2 0 0 2045.9
CH4 0 0 3020.8
C6H6 0 3.4 42.8
C7H8 274.2 82.5 5.3
C12H10 0 1.0 0

The SRK (Soave-Redlich-Kwong) equation of state is a widely accepted thermodynamic

model for hydrocarbon systems, chosen for its accuracy in predicting phase behavior and
properties such as vapor-liquid equilibrium. In our study, the SRK model was specifically selected
from within the Aspen HYSYS software's available thermodynamic models due to its established
reliability and applicability to the toluene hydrodealkylation process.
Variations in this experiment might include:
1. Temperature Variation:
The first experiment involves varying the temperature at the reactor inlet within
the range of 1100 to 1400°F. This variation aims to understand the impact of initial
temperature on the reactor outlet temperature and overall energy consumption.
2. Operating Pressure Variation:
The second experiment includes varying the operating pressure of the reactor
within the range of 20 to 60 atm. The goal is to evaluate how operating pressure affects
the conversion of toluene into benzene and other by-products.
3. Feed Composition Variation:
The third variation involves changes in feed composition, particularly the
concentrations of toluene and hydrogen. This experiment helps understand the
reactor's response to changes in feed composition. This paper will show the results
based on Table 1 Feed Composition.
4. Use of Different Reactor Types:
The last experiment involves using different types of reactors, such as
conversion reactors, catalyst reactors, or reactors with modified designs. This variation
can be done to compare the performance and efficiency of different reactors in the
hydrodealkylation process. However, this paper focused on the use of conversion
reactor only.

RESULTS AND DISCUSSION

Figure 2 shows the process flowsheet in Aspen HYSYS with temperature and pressure
specified for each stream. It appears that the temperature exiting the reactor is 1263 oF (not
1268 oF as in Figure 1). To simplify the calculations, a panel heater (E-101) was used here as a
replacement for the furnace. Then, the type of reactor used is a conversion reactor because it is
known that the conversion of toluene in the reactor is 75%, and 2 mol percent of benzene
remaining after the first reaction is converted into biphenyl (also known as diphenyl).
Table 2 displays the material streams, whereas Table 3 presents the composition of each
flow. Table 4 provides the energy demands for the heat exchanger (E-100) and furnace (E-101).
From Table 2, it is evident that the reactor output has a molar flow rate of 5476 lbmole/hr.

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 Rudy, A., et al., Simulation of the Hydrodealkylation of Toluene Using Conversion Reactor, Keluwih: Jurnal Sains dan
Teknologi, Vol.5(1), 19-26, Februari 2024.
https://doi.org/10.24123/saintek.v5i1.6351

Figure 2. Process flowsheet.

Table 2
Material Streams

Material Streams

Feed Recycle Gas S1 S2 S3 S4 S5

Recycle

Vapour 0 0 1 0.9265 1 1 1 0
Fraction

Temp. F 75 250 120 124 1000 1200 1263 1263

Press. Psia 569 569 569 569 564 494 494 494

Molar lbmole 274.2 86.9 5115 5474 5476 5476 5476 0

Flow /hr

Mass lb/hr 2.53e+4 8021 5.64e+4 8.97e+4 8.97e+4 8.97e+4 8.97e+4 0

Flow

Liquid Barrel 1988 629.1 1.54e+4 1.80e+4 1.80e+4 1.804e+4 1.82e+4 0

Volume /day
Flow

Heat Btu/hr 1.45e+6 1.17e+6 -9.43e+7 -9.17e+7 -2.57e+7 -8.453e+6 -8.45e+6 0

Flow

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Rudy, A., et al., Simulation of the Hydrodealkylation of Toluene Using Conversion Reactor, Keluwih: Jurnal Sains dan
Teknologi, Vol.5(1), 19-26, Februari 2024.
https://doi.org/10.24123/saintek.v5i1.6351

Table 3
Compositions (Component Mole Fractions)

Compositions

Feed Recycle Gas S1 S2 S3 S4 S5

Recycle

Toluene 1 0.9494 0.0010 0.0661 0.0661 0.0661 0.0615 0.0615

Benzene 0 0.0391 0.0084 0.0084 0.0084 0.0084 0.0569 0.0569

BiPhenyl 0 0.0115 0 0.0002 0.0002 0.0002 0.0008 0.0008

Methane 0 0 0.5906 0.5517 0.5517 0.5517 0.6012 0.6012

Hydrogen 0 0 0.4000 0.3736 0.3736 0.3736 0.3246 0.3246

Table 4
Energy Streams

Energy Streams

Q E1

Heat Flow Btu/hr 6.597e+007 1.729e+007

The inlet temperature of the reactor is 1200°F (649 oC), and the outlet temperature (or
temperature within the reactor) is 1263 °F (684 oC) due to the exothermic nature of the reaction.
Meanwhile, the pressure in the reactor is 494 psia (33.6 atm). The recommended operating
temperature and pressure for this reaction are at 500oC – 650oC and 20 to 60 atm pressure
(Liquisearch, n.d.; Wikipedia, n.d.).
The exothermic nature of the hydrodealkylation reaction plays a crucial role in the
overall process dynamics. As toluene undergoes conversion to benzene and other by-products,
a significant amount of heat is liberated. This heat release is attributed to the breaking of
chemical bonds and the formation of new compounds with lower energy states. The
exothermicity of the reaction necessitates careful consideration of temperature control within
the reactor system. Efficient heat management becomes paramount to prevent overheating,
maintain optimal reaction rates, and ensure the stability and longevity of catalysts if used.
Strategies such as heat exchangers, cooling systems, and precise control of feed rates are
employed to manage the exothermic heat generation effectively. Additionally, understanding
the exothermic nature of the reaction aids in designing safer and more efficient industrial-scale
processes, contributing to overall sustainability and process optimization in the petrochemical
industry.
According to Figure 3, altering the initial temperature of the reactor inlet within the
range of 1100 to 1400 F will impact the reactor outlet temperature. This temperature alteration
also affects the utility energy at E1, as shown in Figure 4. However, it is important to note that
this temperature change will not have any effect on the pressure inside the reactor or the molar
flow of vapor (S4). This is because the mass balance calculations adhere to the given conditions
(i.e., the conversion of toluene in the reactor is 75%, and 2 mol percent of benzene remaining
after the first reaction is converted into biphenyl).

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Rudy, A., et al., Simulation of the Hydrodealkylation of Toluene Using Conversion Reactor, Keluwih: Jurnal Sains dan
Teknologi, Vol.5(1), 19-26, Februari 2024.
https://doi.org/10.24123/saintek.v5i1.6351

Figure. 3. Plot the Temperature of S4 vs S3.

Figure 4. Plot of E1 vs S3.

CONCLUSIONS
The simulation of the conversion reactor for toluene hydrodealkylation has
demonstrated the efficiency of conducting mass balance and heat balance calculations using
Aspen HYSYS. These results are instrumental in the initial design phase of a benzene plant
employing the hydrodealkylation process of toluene. The ability to accurately model the process
parameters and assess the energy requirements lays a solid foundation for further engineering
and optimization efforts. Moving forward, future research endeavors will delve into exploring
different reactor types while delving deeper into the kinetics of the hydrodealkylation reaction.
This comprehensive approach will contribute to refining process efficiencies and advancing the
understanding of key reaction mechanisms, ultimately enhancing the overall viability and
sustainability of benzene production processes.

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Rudy, A., et al., Simulation of the Hydrodealkylation of Toluene Using Conversion Reactor, Keluwih: Jurnal Sains dan
Teknologi, Vol.5(1), 19-26, Februari 2024.
https://doi.org/10.24123/saintek.v5i1.6351

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