PRODUCTION OF BENZENE BY HYDRODEALKYLATION OF TOLUENE

INSTITUTO POLITECNICO NACIONAL

ESCUELA SUPERIOR DE INGENIERIA QUIMICA E
INDUSTRIAS EXTRACTIVAS

Production of Benzene by Hydrodealkylation of

Toluene

DR. EDGAR RAMIREZ JIMENEZ

TEAM MEMBERS:
 ILLESCAS SANCHEZ LUIS
ALFREDO
 ORTIZ ALVAREZ JOSE MANUEL
 PINEDA LOPEZ ALINAIT DE
JESUS

INDEX
PRODUCTION OF BENZENE BY HYDRODEALKYLATION OF TOLUENE

ABSTRACT
FINAL PROJECT
HYDRODEALKYLATION OF TOLUENE FOR BENZENE PRODUCTION
This process for this project is the design and simulation of a process for the
hydrodealkylation of toluene to benzene. This typical petrochemical process has been
used in several plants of process, particularly in developing the hierarchical approach of
PRODUCTION OF BENZENE BY HYDRODEALKYLATION OF TOLUENE

process synthesis. Although relatively simple, this case study is very helpful for teaching
the key aspects of conceptual process design
We’ll put together different aspects developed so far with respect to process synthesis and
energy integration, complete the steady-state and dynamic simulation with process control
implementation and finally discuss the quality of design from the perspective of flexibility in
operation with respect to process synthesis and energy integration, complete the steady-
state and dynamic simulation with control process implementation and finally discuss the
quality of design from the perspective of flexibility in operation.

SIMULATION TASK
The main objective to achieve in this task is to obtain benzene by making the simulation
process of HDA of toluene, following the main reactions and getting the kinetic information
from the Arhenius expressions that is give on the problem.
In the reactor we’re going to obtain the conversion of toluene an benzene by putting the
reactor on its maximum permissible temperature that it’s 700°C operating adiabatically so
we have a temperature and pressure specification that says that we need to obtain 620°C
and 35 bar to start the reaction and obtain the convertion of the products from the main
reaction.
For this process, as always, we must be able to achieve a specified production rate of
essentially pure benzene while minimizing yield losses of hydrogen and diphenyl. The
reactor feed ratio of hydrogen to aromatics must be greater than 5:1. The reactor effluent
gas must be quenched to 620°C as we mentioned in the last paragraph.
This process is going to help us to understand the main tools of aspen plus v10 by putting
this process on action, by connecting each of the equipment and streams that we are
having on this simulation.

INTRODUCTION
DESIGN AND SIMULATION OF A HDA PLANT
Benzene is a valuable base chemical product. A major source is the hydrodealkylation of
aromatic feedstock, namely of toluene, available in large amounts by reforming processes.
PRODUCTION OF BENZENE BY HYDRODEALKYLATION OF TOLUENE

The main reaction is the transformation of toluene to benzene in the presence of

hydrogen:
Toluene (T) + Hydrogen (H)  Benzene(B) + Methane (M)
Benzene is definitely very versatile and very important in chemistry because some
compounds derived from it and it is one of the best solvents for iodine, sulfur, phosphorus,
gums, waxes, etc. With its variety of uses and applications this compound is included in
the so-called aromatic compounds.
The HDA process is typical of many chemical process with many chemical components,
many unit operations, several recycle streams, and energy integration
Now the hydrodealkylation of toluene contains nine basic unit operations: reactor, furnace,
vapor-liquid separator, recycle compressor, two heat exchangers, and three distillation
columns.
Two vapor-phase reactions are considered to generate benzene, methane, and diphenyl
from reactants toluene and hydrogen.

C 6 H 5 CH 3+ H 2→ C 6 H 6+CH 4
2 C 6 H 6<→C 12 H 10+ H 2
The kinetic rate expressions are functions of the partial pressures (in psia) of toluene PT,
hydrogen PH, benzene PB, and diphenyl PD, with an Arrhenius temperature dependence.
Zimmerman and York (1964) By-product diphenyl is produced in an equilibrium
[Link] the following rate expressions:

γ 1=K 1 ( T ) PTP H 1/ 2 [=]lbmol/ft3/min, pi[=] psia

γ 2=K 2 ( T ) PB 2 −K−¿2 ( T ) PDPH ¿ [=]lbmol/ft3/min, pi[=] psia

Where

−25616
K 1=3.6858 ×1 06 exp [ T ]
T [¿] K

−25616
K 2=5.987 ×1 0 4 exp [ T ]
T [ ¿] K

−25616
K−2=2.553 ×1 05 exp [ T ]
T [¿ ] K

THERMODINAMICAL MODEL
WHY PENG ROBINSON?
PRODUCTION OF BENZENE BY HYDRODEALKYLATION OF TOLUENE

PENG ROBINSON
A first issue is the thermodynamic modelling. For the high-pressure part including the
stabiliser, an equation of state model is appropriate, as for example Peng-Robinson or
Soave-Redlich-Kwong. A specific model for hydrocarbons, as Chao-Seader or Grayson-
Streed, may be used equally for the low-pressure part.
Peng-Robinson Equation of State is used to model the system, allowing for consistent
physical and chemical energy calculations in both liquid and gas phases in all streams
The Peng-Robinson equation of state is the basis for the PENG-ROB property methods.
The model has been implemented with choices of different alpha functions and has been
extended to include advanced asymmetric mixing rules.
By default, the PENG-ROB property method uses the literature version of the alpha
function and mixing rules. The PR-BM property method uses the Boston-Mathias
alpha function and standard mixing rules. These default property methods are
recommended for hydrocarbon processing applications such as gas processing, refinery,
and petrochemical processes.
Their results are comparable to those of the property methods that use the standard
Redlich-Kwong-Soave equation-of-state. When advanced alpha function and asymmetric
mixing rules are used with appropriately obtained parameters, the Peng-Robinson model
can be used to accurately model polar, non-ideal chemical systems. Similar capability is
also available for the Soave-Redlich-Kwong model.
The equation for the Peng-Robinson model is:

RT a
P= −
( C+ Vm )−b ( Vm +c )( Vm +c +b ) +b (Vm+c −b)

For best results, the binary parameters kij and lij must be determined from regression of
phase equilibrium data such as VLE data. The Aspen Physical Property System also has
built-in kij and lij for a large number of component pairs in the EOS-LIT databank. These
parameters are used automatically with the PENG-ROB property method. Values in the
databank can be different than those used with other models such as Soave-Redlich-
Kwong or RedlichKwong-Soave, and this can produce different results.
PRODUCTION OF BENZENE BY HYDRODEALKYLATION OF TOLUENE

TABLE 1
D.-Y. Peng and D. B. Robinson, "A New Two-Constant Equation-of-state," Ind.

Eng. Chem. Fundam., Vol. 15, (1976), pp. 59–64.

P.M. Mathias, H.C. Klotz, and J.M. Prausnitz, "Equation of state mixing rules

for multicomponent mixtures: the problem of invariance," Fluid Phase

Equilibria, Vol 67, (1991), pp. 31-44.

PRODUCTION OF BENZENE BY HYDRODEALKYLATION OF TOLUENE

INTRODUCTION

PROCESS DESCRIPTION

Feed streams

1. Toluene is available at 42 bara and 25◦C and are to be processed 125 kmol/hr

2. Make-up Hydrogen (95 mol% H2, 5mol% CH4) is available at 42 bara and 40◦C and are to be
processed 178.67 kmol/h of H2.

Feed Effluent, Heat Exchanger and Fired Heater

The gross feed (i.e., fresh feed and recycled streams) is preheated through a countercurrent
feed/effluent heat exchanger and then a fired heater (furnace) before being introduced into the
[Link] effluent from the reactor must be quenched to 620◦C (the maximum permissible inlet
temperature for a heat exchanger) before entering the feed/effluent heat exchanger, and a
portion of the liquid product from the phase separator is used to quench the reactor effluent to
this temperature. Assume a pressure drop allowance of 2.5 bar for the heat exchanger (shell and
PRODUCTION OF BENZENE BY HYDRODEALKYLATION OF TOLUENE

tube sides) and furnace. For shell and tube exchanger, use an overall heat transfer coefficient 50
W/m2K, and assume a ∆Tmin of 10◦C. Assume a 0.35 bar pressure drop allowance for other
exchanger on both shell and tube sides. Cooling water is available and should be used in
preference to air cooling. Cooling water is supplied at 30◦C and the maximum return temperature
is 50◦C.

Reactor

A mixture of fresh Toluene, liquid Toluene recycled from the distillation train, make-up Hydrogen,
and recycled gas is fed to the reactor. The gross feed should be heated to at least 620◦C and 35
bara before entering the reactor. The reactor is adiabatic, with a maximum permissible outlet
temperature of 700◦C. Assume a pressure drop allowance of 2.5 bar. It is desired to obtain a 75%
conversion of Toluene by the first reaction, and 3% conversion of total benzene (i.e., both that in
the feed, and that generated by the first reaction) by the second reaction. Pilot plant runs indicate
that this conversion and selectivity can only be achieved if there is at least 5:1 Hydrogen to oil
ratio on a molar basis at the reactor inlet. Oil refers to the sum of Benzene, Toluene and diphenyl
in the total reactor feed. An excess of Hydrogen reduces coking and improves selectivity. The
reactor type is a plug flow with the following dimensions: length = 10 m and diameter = 2.3 m.

Phase separator

The product mixture leaving the reactor contains a significant amount of unreacted Hydrogen and
Toluene. This Hydrogen and Toluene must be recovered and recycled. As a first step, the reactor
effluent is quenched and then cooled by the feed/effluent heat exchanger. On exit from
feed/effluent heat exchanger, the product mixture is further cooled to 40◦C using a heat
exchanger, and then flashed in a phase separator. The vapor product (rich in Hydrogen and
Methane) is compressed and recycled. A portion of the vapor recycle is vented to purge Methane
from the system. The flowrate of the purge stream is 0.082 times the flowrate of the vapor
product from the flash.

Stabilizer Column

The liquid product from the flash drum is split between a quench stream for the reactor effluent,
and the liquid feed to the distillation column train. First, the liquid feed is stabilized by separating
out the remaining Hydrogen and Methane. The overhead product from the Stabilizer column is
taken off to fuel as vapor at 10 bara and 50◦C. Preliminary design calculations indicate that about
10 theoretical stages are adequate for this separation, and that feed should be introduced onto
the ninth stage from the top of the column. The column should be operated such that mole
fraction of Methane in the bottom product must be less that 0.0002.

Benzene Column
PRODUCTION OF BENZENE BY HYDRODEALKYLATION OF TOLUENE

The bottom product from the Stabilizer column is mainly Benzene and Toluene, but also contains
diphenyl and traces of the gaseous species. The Benzene column splits this mixture to produce and
overhead liquid product stream rich in Benzene, and a bottoms stream rich in Toluene. Preliminary
design calculations indicate that 30 theoretical stages are adequate for this separation, and that
feed should be introduced onto the fifteenth stage from the top of the column. The column is
operated at 1 bara, and such that the mole fraction of Toluene in the distillate is 0.0003, and the
mole fraction of Benzene in the bottoms is 0.015.

Toluene Column

The Toluene column splits diphenyl from the recycled toluene in order to purge it. The overhead
is a liquid product stream rich in Toluene that is recycled and mixed with fresh Toluene feed, and
the bottoms stream is a product stream rich in diphenyl. Preliminary design calculations indicate
that five theoretical stages are adequate for this separation, and that feed should be introduced
onto the second stage from the top of the column. The column is operated at 1 bara, and such
that the mole fraction of diphenyl in the distillate is 0.0003, and the mole fraction of Toluene in
the bottoms is 0.05.
PRODUCTION OF BENZENE BY HYDRODEALKYLATION OF TOLUENE

changes to flowsheet structure and operating parameters

required to make the problem feasible
PRODUCTION OF BENZENE BY HYDRODEALKYLATION OF TOLUENE

FLOWSHEETING CALCULATIONS

DECOMPOSITION STRATEGY
First step was to understand the main functions of each equipment and what was their
relation with the streams connection of the process so with that idea our process was
going to
We started by building the following diagram in the aspen simulator which consist in focus
on the material balance working with the main mixture that take our feed currents to the
reactor, where we found that we have to change the kinetic model to the right unit sets,
that the simulator asks.
So we decided to check our main kinetic model that has to be with the first reaction where
we are going to obtain benzene and methane so with this the convertion that we expect to
have is of 75% of toluene and 3% of benzene and we calculate the right unit sets following
the next calculation algorithm.
FIRST KINETIC MODEL REACTION

γ 1=K 1 ( T ) PTP H 1/ 2 [=]lbmol/ft3 /min, pi [=] psia

Escriba aquí laecuación .

γ1
K 1 ( T )= [=] lbmol/ft3 min psia3/2
PTP H 1 /2
WITH THE NEXT ARRHENIUS MODEL

k 1=3.6858 × 106 exp[−25616/T ]T [¿] K

lbmol/ft3 min psia3/2 to [=] kgmol/m3 sec pa2

SECOND AND THIRD KINETIC MODEL

γ 2=K 2 P B2−K −2 PDPH

−25616 [ ]
k 2=5.987× 104 exp [ T ]
T¿K

k −2=2.553 ×105 exp [−25616/T ]T [¿] K

PRODUCTION OF BENZENE BY HYDRODEALKYLATION OF TOLUENE

With this calculations we put the Kinetic factor and the Activation energy on the reaction
set to start the transformation and determine what was our temperature and pressure that
we need to achieve to obtain the convertion needed.
By putting the conditions in the reactor we are going to be on the phase separator(Flash)
because here we have the recycle streams that comes from a vapor and a liquid stream
where we can accumulate more product that comes from the reactor at the first stage.
After that we’ve noticed that we need to supply the require energy to the reactor to achieve
more temperature to star the reaction we start the second stage
SECOND STAGE:
To start this stage we’ve noticed that we are not having the right temperature to start our
reaction, so we decide to put the furnace before the reactor as we se in the process.
We dediced to do that to start the process, because in many plants to begin the process
they put a furnace can achieve the the reaction temperature but we didn’t connect the
recycle streams that comes from the flash separator because we are not working with that
streams yet, at first we decided that we only need to warm up the mix to start the reaction,
but we didn’t’ have enough success and we checked the kinetics from the first reaction,
and we decided to recalculate again but taking the 700°C that it’s the maximum
permissible temperature of the reactor, so the next change we made to obtain this
temperature was to change the reactor type but not changing the adiabatic form so we just
specified the outlet temperature, after all there’s just a change in the temperature and it
stills working like and adiabatic reactor.
By changing this specification, we decided to start working with the heat exchanger but we
didn’t connect the recycle streams from the flash separator the thing we want to achieve is
the outlet temperature from the reactor.

HEAT EXCHANGER
To start working with this heat exchanger we change the specification from the
PRODUCTION OF BENZENE BY HYDRODEALKYLATION OF TOLUENE