Chemcon 2013

th
66 Annual Session of Indian Institute of Chemical Engineers
Hosted at Institute of Chemical Technology, Mumbai 400 019
27-30 December 2013

Modeling, Simulation and Optimization of Naphtha reforming process on ASPEN Plus

platform
Shubhi Vashishtha, Shweta Sharma, Pratibha Pal, Utkarsh Maheshwari

Department of Chemical Engineering, Birla Institute of Technology and Science, Pilani, Rajasthan-333031, India.
vashishtha13@gmail.com, shwetasharma.tech2901@gmail.com, pratibha.mbd@gmail.com, utkarsh@pilani.bits-pilani.ac.in

Abstract: Naphtha Reforming is an integral part of the petroleum refining industry. It is necessary for obtaining high octane
gasoline from naphtha feedstock. This high octane gasoline is obtained by a nominal presence of aromatic in the C1-C4
fractions present as gasoline. There are a number of reactions involved in the reforming process. Some of the reactions are
favorable for the gasoline production while others are undesirable. The process of reforming aims to the conversion of low
octane component into a high octane component without changing its boiling characteristics.

In the present study, the modelling and simulation of a semi regenerative reforming process has been done on the ASPEN Plus
platform and the best operating conditions of reactor temperature as 550 °F and the hydrogen to hydrocarbon feed ratio as 0.67
have been optimized for the process on the basis of varying parameters. At these conditions we get the best high octane number
gasoline component from naphtha feedstock. These conditions can well be created by combining this endothermic process of
reforming with an exothermic process of hydrogenation of nitrobenzene to get optimal heat integration of the process.

Keywords: Naphtha; reforming; modeling; simulation; optimization.

1. Introduction: low-octane hydrocarbons in the naphtha into more valuable

In petroleum refining and petrochemical industries,
catalytic naphtha reforming is a very important process for
producing high octane gasoline, aromatic feedstock and
hydrogen. Naphtha or cracking oil used as a feedstock in
Catalytic reforming unit to produce high octane value
liquid as main products with hydrogen (H2) and LPG as by-
products . A conventional naphtha reforming process
consists of 3 or 4 reactors in series and heater before each
reactor to reheat the stream into the reaction temperature
range, before entering the next reactor. Shakoor has
reported that catalytic reforming unit's uses industrial
catalysts consisted of Gama Alumina support as an acid
function treated with chlorine in order to increase its
surface acidity [1]. The major chemical reactions during the
catalytic reforming are the following [2]:
1. Dehydrocyclization of paraffins into aromatics.
2. Isomerization of alkylcyclopentanes into cyclohexanes.
3. Dehydrogenation of cyclohexanes into aromatics.
4. Isomerization of linear paraffins into iso-paraffins.
5. Hydrocracking of naphthenes and paraffins and
Hydrodealkylation of aromatics;
1.1 Feedstock
Naphtha is converted into reformate by the catalytic
reforming process. This process involves the conversion of
1
high-octane gasoline components without changing its
boiling point range. Naphtha and reformate are complex
mixtures of paraffins, naphthenes, and aromatics in the C5–
C12 range [3]. Naphthas from catalytic or thermal cracking
also contain olefins. Naphthas of different origin contain
small amounts of additional compounds containing
elements such as sulfur and nitrogen. These elements affect
the performance of the bifunctional noble metal catalyst
used in catalytic reforming and must be removed to low
levels prior to entering the reformer unit. The composition
of hydrocarbons and the concentration of additional
elements determine the quality as reforming feedstock or as
a gasoline blending component.
The major constituent of crude oil or petroleum is a
hydrocarbon. And it accounts for up to 97% of the total
mass. These are paraffinic, naphthenic, or aromatic
structures ranging from light gaseous molecules (C1–C4
alkanes) to heavy waxes or asphaltenic matter. Other than
these compounds, organic compounds of sulfur, nitrogen,
and oxygen, as well as water, salt, and a number of metal
containing constituents such as vanadium, nickel, and
sodium are also the constituent of crude oil. Although
elemental concentrations of carbon and hydrogen vary only
slightly within narrow limits, typically 82–87 wt % and 10–
14 weight % H2, the individual concentrations of the
 Chemcon 2013
th
66 Annual Session of Indian Institute of Chemical Engineers
Hosted at Institute of Chemical Technology, Mumbai 400 019
27-30 December 2013
different compounds that determine the physical properties
are highly variable and depend on the crude oil origin.
Full-range naphtha is the fraction of the crude oil boiling
between 30°C and 200°C, and constitutes typically 15–30%
by weight of the crude oil. This includes hydrocarbons
ranging from C5 to C12, some sulfur, and small amounts of
nitrogen. Metal containing compounds are usually not
present. The naphtha obtained directly from the
atmospheric crude distillation column is termed straight run
(SR). However, naphtha is also produced during processing
of the heavier parts of the crude oil (e.g., Catalytic cracker
naphtha, visbreaker naphtha, Coker naphtha). As opposed
to the straight-run streams, these naphthas also contain
olefinic hydrocarbons. Light naphtha is the fraction boiling
from 30°C to 90°C, containing the C5 and C6
hydrocarbons. Heavy naphtha is the fraction boiling from
90°C to 200°C. The term ‘medium naphtha’ is sometimes
used for the fraction of this heavy cut that boils below
150°C and includes mostly C7–C9 hydrocarbons [5].
1.2 Naphtha reforming processes
Catalytic reforming technologies and processes have been
the subject of numerous discussions and reviews over the
past 50 years seen by Raymond et al. Since the pioneering
work of Vladimir Haensel and UOP on platinum on
alumina catalyst and platforming in the 1940s, catalytic
reforming technology has evolved from semiregenerative,
fixed-bed processes to the more energy efficient, highly
reliable, low operating cost, and continuous catalyst
reforming units.
Typical process objectives are the upgrading of low octane
naphthas to high octane gasoline blending components,
production of aromatic and chemical feedstock, and
production of hydrogen. Over the past five decades,
numerous advancements have been made with respect to
key reforming processes and in the development of high-
performance catalysts. In the current environment of low-
sulfur gasoline and ultra low-sulfur diesel regulations for
reducing air pollutants, catalytic reformers and in
particular, continuous reformers have become
indispensable as support to refiners’ plans for installation
of enhanced processes for hydrotreating catalytic cracker
feed, distillates, and catalytic cracker gasoline. Refiners
will be relying on their catalytic reformers for reliable
hydrogen supply for the various desulfurization processes
required to achieve near-zero-sulfur gasoline and ultra low-
sulfur diesel.
2
To ensure that catalytic reformers perform reliably, both
reactor and catalyst conditions must be maintained. Ren [7]
reported through experimental results that a full recovery of
the activity of the clean catalyst is not achieved by the
regeneration process, and that the quality of regeneration
depends on the coke content reached during the
deactivation /regeneration cycle.
1.2.1 Catalytic reforming process
Reforming processes are usually classified as
semiregenerative, cyclic (fully) regenerative, and
continuous (moving-bed) regenerative processes based on
their mode of operation, severity, and mode of
regeneration. A short review of the reforming processes is
provided in [5].
1.3 Licensed reforming processes
Catalytic naphtha reforming is the technology that
combines catalyst, hardware, and process to produce high-
octane reformate for gasoline blending or aromatics for
petrochemical feedstock. Reformers are also the source of
much needed hydrogen for hydroprocessing operations.
Several commercial processes are available worldwide, and
the licensing of technology for semiregenerative and
continuous reforming is dominated by UOP and Axens
(formerly IFP) technologies [5].
Table 1: Operating parameters for flowsheet [6]
Operating parameters Range
Naphtha feed stock 30410 kg/hr
Temperature of reactor 470 °F
Typical properties of catalyst
dp 1.2 mm
sa 220 m2/g
ϵ 0.36
2. Material and Methods:
Optimization of naphtha hydrotreating processes has been a
major concern of the industries with studies like Sepehr et
al. In conventional fixed-bed reforming the naphtha
(middle distillates of an atmospheric distillation column or
condensate from gas reservoirs) feedstock is combined with
a recycle gas stream contain 60%-90% (by mole) hydrogen
[9]. Hydrogen can adjust the H2/HC ratio through the
reactors to reduce the coke formation and also it sweeps the
products through the catalyst pores. The total reactor
 Chemcon 2013
th
66 Annual Session of Indian Institute of Chemical Engineers
Hosted at Institute of Chemical Technology, Mumbai 400 019
27-30 December 2013
charge is heated and passed through the catalytic reformers,
which are designed with three adiabatically operated
reactors and three kilns between the reactors to maintain
the reaction temperatures at design levels. The effluent
from the last reactor is cooled, and then enters the product
separators. The off gases and reformates are separated from
the above and bottom of the separator, respectively. Figure
3 shows the ASPEN Flowsheet of the process. The
naphtha feed is sent to pump1 from where it is pumped to
mixer1 and mixed with hydrogen recycle in the desired
ratio. It is then sent through a heat exchanger and series of
furnaces before being fed into the reactors, to raise the
streams up to the required reaction temperature. The
reactors work on specified input conditions. The product
moves through the reactors and is cooled and stabilized
after which the column1 fractionates the product to get
reformate1 as gasoline and reformate2 as heavier
hydrocarbons. This gasoline has a small percentage of
aromatics present in it to give the gasoline a good octane
number.
2.1 Reaction kinetics:
Considering the simplified model suggested [2], four
dominant idealized reactions can be used to describe the
catalytic reforming process so that the catalytic reforming
system can be simplified significantly. The reactions are as
follows [2] :
1) Dehydrogenation of naphthenes to aromatics
Naphthenes (CnH2n) ---> Aromatics (CnH2n6)+3H2
2) Dehydrocyclization of paraffins to naphthenes
Naphthenes (CnH2n) + H 2 ------> Paraffins(CnH2n+2)
3) Hydrocracking of naphthenes to lower hydrocarbon
Naphthenes (CnH2n) +n/3 H2 ------> Lighter ends (C1-C5)
4) Hydrocracking of paraffins to lower hydrocarbon
Paraffins (CnH2n+2)+(n-3)/3 H2 ----->Lighter ends (C1-C5)
The reaction rate constants, equilibrium constants,
activation energies and standard heat of reaction are have
been taken from reported literature and suitable
assumptions have been made where necessary. The
reaction rate constant and equilibrium constants are
temperature dependent.
3. Results and Discussion
3
On the modeling and simulation of the whole process
according to the specified conditions, we have studied the
varying effect of temperature and hydrogen to naphtha feed
ratio. On varying the parameters in a particular operable
range the corresponding reformate compositions were
calculated and the best operating conditions for the process
were judged.
3.1 Effect of temperature on naphtha reforming process
At keeping the feed flow rate of 30410 kg/hr constant, we
varied the reactor temperature range between 350 to 550
°F, above and below which the process becomes inoperable
for the other specified parameters. It was observed that as
the temperature increases, the composition of aromatics in
the gasoline which comes out of reformate1 in the
flowsheet also increases (Figure 1).
Similarly the composition of lower hydrocarbons also
increases with temperature. With increasing temperature
along the first reactor, product yield increases slowly and
for second reactor main product yield increases sharply.
This is because the naphtha cracking reactions are
endothermic. The reaction rate accelerates with increase in
temperature (Figure 4). Most of the reactions are performed
in the second reactor so that the aromatic concentration
increases in the second reactor.
3.2 Effect of hydrogen to naphtha feed ratio on naphtha
reforming process
We keep the reforming process functional at a constant
reactor temperature of 470°F while we vary the feed flow
rate from a range of 29605 to 40000 kg /hr. The hydrogen
rate is kept 50 kg/hr. The composition in reformate1 of
aromatics as well as lower hydrocarbons increases with the
feed ratio (Figure 5).
Figure 1: Effect of temperature on the composition of
aromatics in gasoline
 Chemcon 2013
th
66 Annual Session of Indian Institute of Chemical Engineers
Hosted at Institute of Chemical Technology, Mumbai 400 019
27-30 December 2013

Figure 2: Process Flowsheet of Semi Regenerative Catalytic Naphtha Reforming Process [2]

Figure 3: ASPEN Flowsheet of the naphtha reforming

4
 Chemcon 2013
th
66 Annual Session of Indian Institute of Chemical Engineers
Hosted at Institute of Chemical Technology, Mumbai 400 019
27-30 December 2013
Figure 4: Effect of temperature on the composition of
lighter hydrocarbons in gasoline
Figure 5: Effect of feed ratio on the composition of
compounds in gasoline
4. Conclusions:
In this paper we have a naphtha reforming model which has
been simulated using ASPEN Plus platform under the
operating conditions determined from the literature. The
whole process flowsheet has been developed and the
parameters of temperature and hydrogen to feed ratio has
been varied to study its effect on the aromatics and lower
hydrocarbons present in the gasoline. The process has been
studied and optimized to get the best operating condition at
temperature of 550 °F and the hydrogen to hydrocarbon
feed ratio as 0.67. At these conditions we get the best high
octane number gasoline component from naphtha
feedstock. These conditions can well be created by
combining this endothermic process of reforming with an
exothermic process of hydrogenation of nitrobenzene to get
optimal heat integration of the process.
References
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Rahimpour., “A comparison of two different flow types on
performance of a thermally coupled recuperative reactor
containing naphtha reforming process and hydrogenation of
nitrobenzene”, Journal of hydrogen energy, 36 (2011)
3483–3495.
[3] H. Weifeng, S. Hongye, H. Yongyou, C. Jian,
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[7] X. H. Ren, M. Bertmer, S. Stapf, D.E. Demco, B.
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