Predictive Modeling and Optimization For An Industrial Penex Isomerization Unit A Case Study

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Article
Predictive Modeling and Optimization for an

Industrial Penex Isomerization Unit - A Case Study
Mohanad M. Said, Tamer Samir Ahmed, and Tarek M. Moustafa
Energy Fuels, Just Accepted Manuscript Publication Date (Web): 23 Nov 2014
Downloaded from http://pubs.acs.org on December 1, 2014
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Predictive Modeling and Optimization for an Industrial Penex

Isomerization Unit - A Case Study
Mohanad M. Saida, Tamer S. Ahmeda,*, Tarek M. Moustafaa
a
Chemical Engineering Department, Faculty of Engineering, Cairo University

Giza 12613, Egypt
* Corresponding author: Tel.: +20 114 292 4407; E-mail address:
Tamer.S.Ahmed@cu.edu.eg
Abstract. This work presents a model for UOP Hydrogen Once Through (HOT) Penex
Process using Aspen HYSYS Petroleum Refining module. The model relies on routinely
taken industrial data of process streams during normal operating conditions. Acquired data
sets have been tested and screened to ensure data validity for building the model and avoiding
erroneous results. A reaction network with 20 reactions and 19 components has been used for
the reactors model. The reactors model has been validated using 4 months of industrial plant
data. In addition, rigorous tray-to-tray simulation of isomerate stabilizer has been utilized to
match the performance of plant stabilizer. The model validated has been used for studying the
effects of each process variable on plant performance. In addition, the model has been used in
optimizing the operating conditions of the process. This optimization showed a potential for
notable fuel savings in the process.
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1. Introduction
Since the 70s, elimination of lead compounds from gasoline pool has increased
interest into the isomerization of light straight run naphtha so as to preserve the octane
number of produced gasoline1. Recent and future regulations put strict limits on benzene and
aromatic levels in motor gasoline. For example, the U.S. Environmental Protection Agency
MSATII (Mobile Sources Air Toxics Phase 2) regulations requires decreasing the average
benzene content of U.S. gasoline pool to 0.62 vol.%2,3. This urged refiners to search for other
sources of gasoline with a lower aromatic content than catalytic reforming. Isomerization is
thought to be one of the effective solutions to produce motor gasoline compatible with
environmental regulations. Isomerate (isomerization product) is highly desirable with respect
to environmental regulations due to its zero benzene content and high octane number.
Isomerization reactions are exothermic equilibrium-limited reactions. As conversion
is far from equilibrium conversion, an increase in reactor temperature leads to increase in
reaction velocity and subsequent increase in conversion. However, once equilibrium is
approached, increasing temperature decreases conversion due to the decrease of reaction
equilibrium constant4. Figure 1 shows the change of conversion (iso-paraffins yield) with
temperature. As indicated in Figure 1, conversion increases with temperature until a certain
temperature (optimum temperature) is reached, then iso-paraffins yield decreases.
INSERT FIGURE 1
Currently, three catalyst types are used commercially for naphtha isomerization
(Figure 2). All of them are platinum containing catalysts6: 1) Zeolite catalysts: zeolite
catalysts have the lowest activity among isomerization catalysts, hence they are used at
higher temperatures that are unfavorable with respect to isomers yield. However, these
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catalysts have high resistance to feed impurities and can be regenerated. Zeolite catalyst units
use fired heaters for feed and hydrogen heating up to the reaction temperature. The process
also employs a high ratio of hydrogen to hydrocarbon for hydrotreating and dearomatization
of feedstock. Accordingly, a recycle gas compressor and a product separator are used; 2)
Chlorinated alumina catalysts: These are the most active isomerization catalysts providing the
highest octane number and isomerate yield. These catalysts require continuous injection of a
chlorine compound (CCl4) to maintain catalyst activity. In addition, they are very sensible to
impurities (oxygen, sulfur and nitrogen compounds). Therefore, feed hydrotreating and
drying is a mandatory. Low hydrogen to hydrocarbon ratio is required. Hence, neither a
recycle gas compressor nor a recycle gas is needed; 3) Sulfated zirconia: These catalysts have
the advantages of both previous types. They are more active than zeolite catalysts, hence
favoring higher isomers conversions. In addition, they are resistant to impurities and
regenerable. However, units using sulfated zirconia need a recycle gas compressor and a
product separator.
INSERT FIGURE 2
As seen in Figure 2, chlorinated alumina catalysts provide the highest octane number
and isomerate yield. By good operation of upstream hydrotreating unit and feed dryers, a long
service life (more than 10 years) could be achieved2. UOP and Axens are the licensors of
processes using chlorinated alumina-based catalysts. UOP licenses the process under the
name of "Penex Process". The first Penex process was brought on stream at Borger Texas
Refinery using I-3 catalyst7.
Most of the literature concentrates on developing new types of catalysts8. A few
research work paid attention to kinetic modeling of isomerization reactions and a fewer paid
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attention to modeling isomerization reactions over chlorinated alumina catalysts.

Consequently, optimization for industrial isomerization units is very scarce in the open
literature since the rigorous kinetic modeling for the reactor is the heart of the optimization
process. Besl et al.9 discussed briefly the optimization of Penex process in a German refinery.
On the other hand, Dudley and Malloy10 developed a simple kinetic model based only on
isomerization and cracking reactions that was used in optimizing a process that uses AlCl3
liquid catalyst. Ahari and coworkers11 investigated the effects of methyl cyclopentane in the
feed of isomerization feed using a process model developed by HYSYS. In addition, they
studied experimentally the hydrogen partial pressure effect on Pt mordenite zeolite catalyst
activity and conversion of n-paraffins and proposed kinetic equations for n-C5 and n-C6
conversion12. Brito et al.13 studied experimentally the performance of Pt-Ni/mordenite zeolite
catalysts with different metal proportions and kinetic model for catalyst deactivation was
proposed. Koncsag et al.14 proposed a kinetic model for C5/C6 isomerization over Pt/Hzeolite at industrial conditions. Surla et al.15 used a single event methodology to establish a
kinetic model for C5/C6 isomerization over chlorinated alumina catalyst. Finally, a detailed
kinetic model that is suitable for the three major catalyst types was proposed by Chekantsev
et al.8. The reaction network they proposed contained 36 reactions. The authors illustrated
that the differences in reaction rates over different catalysts are modest except for few
isomerization reactions. The model they proposed agreed well with experimental results of
the three catalyst types.
Very little attention was paid in the literature to the application of kinetic modeling
and optimization to an existing industrial unit. In this context, we present here kinetic
modeling for an existing industrial Penex isomerization unit using Aspen HYSYS Petroleum
Refining isomerization reactor model. In addition, the model has been used for studying the
effect of different process variables on process performance and for process optimization.
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2. Process Description
Figure 3 shows a process flow diagram for Penex process. Feed naphtha and make-up
hydrogen first pass through driers to eliminate any traces of water because water is a
permanent poison of Penex catalyst. Then, naphtha and hydrogen are mixed prior to heating
the mixture up to reaction temperature. Maintaining a proper hydrogen partial pressure is
required inside the reactor to prevent coke deposition on catalyst. The reactor charge mixture
is heated by exchanging heat with the second and first reactor effluent, respectively. A
chlorine compound "CCl4" is injected into the reactor charge to provide acid sites on
catalyst's surface that is required for isomerization reaction. The feed is brought up to the
reaction temperature through a fired heater. The effluent of the first reactor is then cooled
through exchangers prior to entering the second reactor to remove heat generated by
exothermic reactions in the first reactor bed so that to favor equilibrium limited isomerization
in the second reactor bed. The reactors' effluent is then fed to a stabilizer to separate light
gases (C4- and hydrogen) from the product stream. The overhead gases is sent to a packed
bed scrubber that employs a caustic wash to neutralize hydrogen chloride formed from the
decomposition of the chlorine compound. Finally, the produced gases are sent to vapor
recovery for LPG production. The stabilized isomerate may be sent directly to gasoline pool
or may undergo fractionation to maximize the octane number of the isomerate.
INSERT FIGURE 3
3. Process Chemistry
Praffin Isomerization. Paraffin isomerization is the main reaction in the process. As
mentioned before, paraffin isomerization is an exothermic equilibrium limited reaction so that
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a higher conversion is favored at low temperatures. Table 1 lists the research octane numbers
(RON) of n-C5 , n-C6 and their isomers. It is clear that multi branched isomers such as 2,2-dimethyl butane (2,2 DMB) and 2,3-dimethyl butane (2,3 DMB) have higher octane numbers
than single branched isomers such as 2-Methyl Pentane (2MP) and 3-Methyl Pentane (3MP).
Thus, formation of multi-branched isomers is highly desirable.
INSERT TABLE 1
Naphthenes isomerization. Naphthene isomerization reaction is also an equilibriumlimited reaction. Cyclohexane (CH) and methylcyclopentane (MCP) exist in equilibrium at
reaction conditions but formation of MCP increases as temperature is increased.
Benzene Saturation. Benzene saturation to cyclohexane is a highly exothermic rapid

reaction. The high heat of reaction of benzene saturation affects the conversion of the
exothermic isomerization reaction that is favored at low temperature. This puts a limit on the
amount of benzene that can be tolerated in reactor feed. All benzene in the feed is saturated
completely in the lead reactor. Actually, the lead reactor temperature is always adjusted to
maximize isomer ratios. If the benzene content of feed increases then a lower reactor inlet
temperature is used to maximize isomers' conversion attained at lead reactor outlet and vice
versa.
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Naphthene ring opening. Naphthenes may undergo ring opening and form paraffins
at reactor conditions. Ring opening increases with increasing reactor bed temperature.
Hydrocracking. As reactor temperature increases, hydrocracking rate increases.
Large molecules (C7) are easier to crack than smaller molecules. As C5/C6 isomerization
approaches equilibrium, the extent of hydrocracking increases leading to lower liquid yield
and an increase in stabilizer overhead gas (C4-).
4. Reactor Model
Aspen HYSYS v. 7.3 Petroleum Refining isomerization reactor module was used in
developing the process model. The module contains a detailed kinetic model of reactions that
occur in isomerization process. The reactor model contains rate equations for isomerization,
benzene saturation, ring opening, hydrocracking, and heavy (C7+) reactions (Figure 4). The
rate expression for each reaction class is coded to match literature data. All reactions are
irreversible except for isomerization and benzene saturation. Typically, the reaction network
consists of 20 reactions and 8 of them are reversible. Each reaction class is first order with
respect to the primary reactant and reaction-class rate equation has a denominator following
Langmiur-Hinshelwood-Hougen-Watson
mechanism.
The
reaction
scheme
contains
hydrocarbons up to C7. Higher carbon components are mapped into six ring C8 naphthenes. In
reality, isomerization feed usually contains trace amounts of C7+ components. Reaction rate
equations are expressed in the model as:
Reaction Rate = Global activity Reaction-class Activity Heterogeneous
(1)
Reaction Rate
Reactor model can be tuned to match plant reactor performance via two schemes:
basic tuning and advanced tuning schemes. Basic tuning includes the tuning of the activity
parameters of the reactor such as global activity (overall reactor activity) and specific
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reaction-class activity parameters (activity of each type of reactions, e,g,: hydrocracking class
reactions). Global activity parameter affects the rates of all the reactions. On the other hand,
the activity of each specific reaction-class can be adjusted via the specific reaction-class
activity parameter (e.g.: hydrocracking activity parameter for hydrocracking-class reactions).
If basic tuning is not sufficient, kinetic parameters of each individual reaction may be tuned
to match plant performance using the advanced tuning.
The Penex unit under investigation is a HOT (Hydrogen-Once-Through unit). The
process flow diagram of the unit is identical to that shown in Figure 3. The current work is
only concerned with the isomerization reactors and the downstream stabilizer. Dryers and gas
scrubber modeling are beyond the scope of this study. No changes or special procedures were
applied for building the model and the model was calibrated according to samples that are
routinely taken during normal operation.
INSERT FIGURE 4
Industrial Data. Data from the industrial unit under investigation were gathered and
were organized into data sets. Each data set represents an operating day. Each data set
includes a component analysis of all input and output streams (make-up hydrogen, feed
naphtha, isomerate and stabilizer off-gas) and component analysis of the lead reactor product.
In addition, each data set includes the operating conditions of the reactors and the stabilizing
column.
C7+ de-lumping. Isomerization feed usually contains a little amount of C7+
hydrocarbons and this amount could be controlled via the upstream naphtha splitter. Figure 5
shows the varaiation of the amount of C7+ in feed during study. The C7+ is mostly around 1
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wt%. The C7+ lump in isomerization feed is expected to be mostly normal heptane, heptane
isomers and C7 naphthenes, with almost no toluene since the boiling point of toluene is
110C, which is far from that existing in the isomerization feed.
For accurate representation of C7+ lump, the de-lumping procedure developed by
Riazi18 was used for the C7+ lump in the current study. The procedure uses correlations for
estimating the paraffins, naphthenes and romatics (PNA) composition of petroleum fractions
using only bulk properities such as specific gravity (SG) and molecular weight (MW). The
results of PNA composition calculations for C7+ in feed are presented in Table 2. The results
reinforce the postulation that toluene is negligable in the isomerization feed. Therefore, the
C7+ fraction is de-lumped into C7 paraffins and C7 naphthenes with known percentage of each
hydrocarbon class.
INSERT FIGURE 5
INSERT TABLE 2
Properities of a petroleum fraction of known composition could be calculated from

the properities of constituent pure components by applying the proper mixing role:

=
(2)
Using this principle, an optimization algorithm can be used to estimate the

composition of a petroleum fraction by minimizing the error between the known properities
of that fraction and the calculated properities. In this work, the following objective function
was minimized:
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=

100

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(3)
This is the same principle that was used in the literature to estimate the composition
of catalytic reformer feed19,20. However, in the current work, a limited number of properties
of C7+ are available (SG, MW, Reid Vapor Pressure (RVP) and RON). This limits the number
of compositions that can be estimated.
Using the preliminary de-lumping obtained through PNA composition calculation,
two additional equations were added for compositions estimate. In this work, the C7+ fraction
was de-lumped into five pesudo components: multi-branched heptane paraffins (MBP7),
single branched heptane paraffins (SBP7), normal heptane (NP7), five ring C7 naphthenes
(5N7), and six ring C7 naphthenes (6N7). Properties of these pesudo components were
obtained from Aspen properities data bank. Mole fractions of pesudo components were used
for the calculation of RVP and MW and volume fractions were used for SG and RON. Table
3 shows a comparison between available properities and calculated properities for C7+ in feed
and product streams. Estimated compositions of C7+ are shown in Table 4.
INSERT TABLE 3
INSERT TABLE 4
Data Screening. Model quality depends mainly on the data used. As indictaed earlier,
data sets used for developing this process model were obtained during normal operation
.Obtaining consistent data from industrial units may sometimes be an extreme difficult
mission due to frequent changes in feed and process conditions. Data sets in days that
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witnessed any up-normal changes in process operation were excluded. In addition, a mass
balance test was applied to all data sets and any data sets having a mass balance error more
than 2% were excluded. In order to ensure data verification, a hydrogen balance was applied
also to data sets by calculating the hydrogen weight in each stream through summing the
hydrogen contribution of each component and any sets having an error more than 3% were
omitted. Taskar and Riggs20 used the following formula to calculate the weight fraction of
hydrogen in component CiHj (H factor):
=

+
(4)
The weight of hydrogen in each stream could be calculated by:

!"#$ $ %#& ' = &%% ( # %#& '
(5)
Apart from data sets in days that witnessed capacity changes, most data sets were
quite consistent having an average mass balance and hydrogen balance error of -0.969% and
-1.481%, respectively.
Model Calibration and Parameters Estimation. Parameter estimation is the most
critical step in model building. A well-calibrated model produces significant and repeatable
predictions over a wide range of operating conditions. Improper calibration of reactor model
may lead to an over calibrated model with a poor predictive power. Aspen HYSYS
isomerization reactor model enables user to match plant performance through basic tuning
and advanced tuning by adjusting kinetic parameters for each reaction. Model developers
claim that basic tuning of reactor model is sufficient to match plant data. In this work, a basic
tuning scheme was applied in order to avoid over calibration of reactor model. Advanced
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tuning may require extremely accurate plant data that were not feasible in our case. For
accurate representation of plant reactor, the upcoming steps were followed:
A- Generating streams:
Each data set was used to generate a stream representing the lead reactor charge at the day
that each data set represents.
B- Running the model:

The reactor model requires some mechanical data to run. These data include reactor
dimensions and catalyst properties (catalyst bed porosity and bulk density).Then the model is
allowed to run generating an output stream.
C- Model calibration:
Reactor model calibration is mainly adjusting the activity parameters to match plant data. In
this work, the reactor model was calibrated with the aid of Aspen HYSYS Optimizer by
minimizing the following objective function:

f*+ = * *,-./0 1/230 +4 + + 57,-./ 71/23 8
(6)
Table 5 lists the adjustment factors used for reactor model calibration and applied
bonds for each parameter. It was found that acceptable model performance is reached when
using those bonds during calibration. It is important not to include yields of all components in
reactor calibration. Pashikanti and Liu21 showed that including all measurements in reactor
calibration may result in a poor calibrated model that responds wildly even to small changes
to input variables. Table 6 shows the reactor measurements that were included in
optimization function and weighting factors used with them.
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INSERT TABLE 5
INSERT TABLE 6
Larger weighting factors were applied for terms where a closer fit is required. For
example, the reactor model is required to fit the plant isomer ratios. Therefore, larger
weighting factors were applied to normal and iso-paraffins. On the contrary, the lowest
weighting factor was given to reactor temperature rise since the lead reactor temperature is
frequently adjusted to maximize isomer ratios in the reactor effluent and hence the reactor
temperature rise usually fluctuates during operation. In the available data sets, an average of
reactor inlet and outlet temperature is only given. Therefore, temperature rise may be the least
reliable data point in each data set and applying a high weighting factor for temperature rise
may result in poor calibration.
The three previous steps were repeated for each data set and activity parameters were
calculated for each data set individually. Almost all activity parameters were found to vary
within a narrow range for different data sets. Consequently, the average values of calculated
activity parameters are expected to be quite satisfactory for model calibration.
The same procedure was used for lag reactor calibration. The composition of the
effluent of the calibrated lead reactor was used to simulate the composition of lag reactor feed
at plant conditions. The lag reactor was calibrated by minimizing error between model and
plant data using the same objective function. Routine sampling in the industrial unit does not
include a sample for lag reactor effluent. Thus, the composition of lag reactor effluent was
calculated through back-mixing of isomerate and stabilizer off-gas streams. The same activity
parameters were used for model calibration and same bonds were used except for global
activity parameter. In isomerization units, the lead reactor catalyst loses activity before lag
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reactor. When lead reactor performance becomes unsatisfactory, catalyst in the lead reactor is
replaced with fresh catalyst and the order of reactors is reversed that the new loaded lead
reactor lags the existing lag reactor (which is now the lead reactor). Therefore, lag reactor
catalyst is always more active than lead reactor catalyst. Due to this fact, a higher upper bond
was given to global activity parameter during lag reactor calibration. Table 7 shows the
average activity parameters estimated through calibration process for both reactors.
INSERT TABLE 7
Model validation and testing. Figures 6 and 7 show the model performance versus
plant yields for the 23 data sets used in reactor model calibration process for lead and lag
reactors, respectively. The model predications are satisfactory for both reactor. It should be
noted that a closer fit may be achieved with advanced tuning of kinetic parameters (especially
the rate constants of ring opening reactions). However, advanced tuning requires strict plant
measurements, which were not available.
INSERT FIGURE 6
INSERT FIGURE 7
In order to ensure model capability of predicting plant performance, the model yields
were compared with plant yields for the next 4 months after calibration. Chlorinated alumina
catalysts lose activity very slowly during normal operation (the catalyst used in the industrial
unit under investigation was loaded from about 13 years and is still being used with good
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activity). Thus, changes in catalyst activity during the 4 months are negligible and recalibration of reactors' models is not required. Figures 8 and 9 show that the model was
useful in tracking plant performance for the 4 months after the calibration.
INSERT FIGURE 8
INSERT FIGURE 9
Stabilizer Model. Although this study is concerned with the optimization of process
variables of reaction section only, a precise stabilizer model is also required for accurate
prediction of isomerate yield. The standard inside-out method was used for stabilizer model22.
The inside-out method converges quickly with a wide variety of specifications. Since the
isomerate stabilizer is used to adjust the RVP of isomerate product by limiting the amount of
C4- in the isomerate product, it functions very similar to the function of a de-butanizer
column. Data provided by Kaes23 show that the overall efficiency of a de-butanizer is 8590%. Since actual plant stabilizer has 30 trays, the model stabilizer should contain about 26
theoretical trays.
According to the guidelines provided by Kaes23, stabilizer specifications were
adopted. The function of isomerate stabilizer is to stabilize isomerate product by separating
light ends from it. Therefore, the RVP of isomerate is an indication of the recovery of light
ends and degree of separation achieved. Since the stabilizer operates with full reflux, another
specification was needed for building stabilizer model. Therefore, the overhead condenser
temperature was specified as a performance specification since the condenser operates with
significant vapor product flows23. Figure 10 shows a complete process flow diagram of the
process model.
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INSERT FIGURE 10
5. Process Variables
Having established a process model for Penex unit, the next step is studying the effects of
each process variable to predict the process performance for a given change in a process variable.
Studying the effects of each process variable is essential for process optimization. The following
study was conducted using the average composition of industrial unit feed during the study
period (6 months).
Lead Reactor Inlet Temperature. Isomerization reactions are equilibrium limited
reactions; hence there is a maximum conversion (equilibrium conversion) that could be attained
at each temperature (Figure 1). Because isomerization reactions are exothermic, the equilibrium
conversion decreases as temperature increases. Whenever the reaction is far from equilibrium
conversion, an increase in temperature leads to increase in reaction velocity and an increase in
conversion (isomers yield and hence RON). However, once equilibrium is reached, increasing
temperature increases backward reaction velocity and reduces conversion. This is reflected in
Figure 11A, which shows the effect of lead reactor temperature on RON. Actually, i-pentane and
2,2-DMB are the components with the greatest effect on RON of isomerate. Therefore, the effect
of temperature on (I-C5/C5)% and (2,2-DMB/C6) are identical with that of RON (Figure 11B
and 11C). Although, the isomerization of 2,3-DMB is still far from equilibrium (Figure 11D), but
it has little effect on RON. In addition, increasing temperature increases the rate of other
reactions. Increased hydrocracking and ring opening reactions leads to increased hydrogen
consumption (Figure 11E). Finally, the increase in hydrocraking leads to the decrease of of
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isomerate yield (Figure 11F). Isomerate wt.% was defined in this study as the wt% of isomerate
to the total reactor effluent.
INSERT FIGURE 11
Lag Reactor Inlet Temperature. For the lag reactor, the effect of the inlet temperature
is similar in trend to that of the lead reactor (Figures 12 A-F).
INSERT FIGURE 12
Hydrogen to hydrocarbon mole ratio. Hydrogen is required for completing the

reactions and decreasing coke deposition on catalyst surface. Generally, increasing inlet
hydrogen leads to higher hydrogen partial pressure inside the reactor which increases
hydrocracking. Consequently, isomerate yield (Figure 13A) and the RON of isomerate (Figure
13B) decrease due to increased hydrocracking of paraffins isomers (lower paraffin Isomerization
Number (PIN = i-C5/C5 + (2,2-DMB+2,3-DMB)/C6)) (Figure 13C)). Therefore, the reactors
should be operated at the lowest possible hydrogen to Hydrocarbon (H2:HC) ratio. However, at
any instance, the H2:HC ratio should not be lower than 0.05 mole H2/mole Hydrocarbon as
claimed by process licensor. The H2:HC mole ratio is usually measured at reactor outlet for
Hydrogen Once Through Penex units.
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INSERT FIGURE 13
Feed rate (LHSV). At the same reactor inlet temperature, the lower the liquid hourly
space velocity (LHSV), the higher the PIN (Figure 14A). On the contrary, the higher the LHSV,
the higher the yield of isomerate due to lower hydrocracking (Figure 14B). This is expected since
increasing feed rate decreases contact time with catalyst, which results in lower reactions rates.
INSERT FIGURE 14
Feed composition. A) Methylcyclopentane and cyclohexane: Generally, cyclic

compounds adsorb on catalyst surface reducing active sites available for other reactants. Hence,
an increase in methylcyclopentane (MCP) and cyclohexane (CH) % causes slightly lower isomer
ratios in isomerate (Figures 15A and 15B). On the other hand, the RON of isomerate will be
higher due to the increase of MCP or CH in isomerate, which has a relative high RON (Figures
15C and 15D). This contradicts what was reported by Ahari et al.11. They investigated the effects
of MCP in isomerization feed and claimed that increasing the amount of MCP in feed results in
reduction of isomerate RON. However, the authors carried out that study using a mixture of nhexane and MCP as a feed on a different catalyst operating at higher temperature. Therefore, at
these conditions, the naphthene isomerization reaction is driven strongly in the direction of
forming CH, which has a relatively lower RON compared to MCP and multi-branched hexane
isomers. In addition, the higher operating temperature leads to increased ring opening of MCP
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and CH, which lead to lower RON. Accordingly, the differences in feed composition and
operating conditions may be the reason for the contradicting results.
Isomerate yield increases with the increase of MCP or CH content in feed. Both cyclo
components do not undergo hydrocracking as paraffins, however ring opening reactions may
occur. Generally, ring opening reaction is favored slightly compared to hydrocracking with
increasing temperature, because of its higher activation energy (e.g. MCP ring opening has a
higher activation energy compared to C6 paraffins hydrocracking). Moreover, reduction of active
sites available for paraffins reduces paraffins hydrocracking, and hence increases liquid yield
(Figures 15E and 15F).
Methylcyclopentane and cyclohexane are also major hydrogen consumers through ring
opening. Therefore, hydrogen consumption increases as the amount of MCP or CH in the feed
increases. It should be noted that the overall hydrogen consumption may not increase (Figures
15G and 15H) due to that the increase of MCP or CH content in feed is on the account of other
components including benzene that is the major hydrogen consumer. However, the hydrogen
consumption in the lag reactor shows an increase with the increase in MCP or CH content
(Figures 15I and 15J).
INSERT FIGURE 15
B) Benzene: Figure 16A shows the actual variation of benzene content in the feed. As
mentioned earlier, benzene is hydrogenated completely to CH in the lead reactor. Benzene
saturation is highly exothermic reaction that is unfavorable by the equilibrium limited
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isomerization. Figure 16B shows the effect of feed benzene content on the lead reactor
temperature rise. Small changes in feed benzene content greatly affect the lead reactor
temperature rise. However, this does not affect isomerate RON much (Figure 16C) since benzene
is converted to CH that has a moderate RON or may undergo isomerization to form MCP that
has higher RON.
On the other hand, the exothermic heat of benzene saturation affects PIN significantly
(Figure 16D). In actual operation, the lead reactor inlet temperature is always varied in order to
maintain a constant temperature rise through the reactor bed. The allowable temperature rise is
increased with feed rate in order to obtain a reasonable conversion of normal paraffins. This
operating scheme may be effective but it is very tedious, especially when wide variations in feed
benzene content occur.
Moreover, the increase in feed benzene content leads to an increase in isomerate yield
(Figure 16E) since the produced CH or MCP undergo slow ring opening and adsorb on catalyst
surface reducing active sites available for praffins hydrocracking. Finally, benzene saturation is
the major hydrogen consuming reaction in Penex process. Figure 16F shows the increase in
hydrogen consumption with increase of benzene in feed.
INSERT FIGURE 16
6. Model application to process optimization

From previous analysis, it can be concluded that feed composition and feed rate are the
dominant process variables. Benzene composition may be the most important variable. As seen
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in Figure 16D, at constant inlet temperature to the lead reactor, the PIN is greatly affected by
variation of feed benzene content. Thus, continuous monitoring of feed benzene content is
always required. Although, feed benzene content does not change widely (Figure 16A), even a
small change in benzene has a great impact on isomerization degree. Refiners offset this impact
by continuous variation of lead reactor inlet temperature so as to obtain a fixed temperature rise
through lead reactor. The amount of allowable temperature rise is increased as feed rate increases
to increase reactions rates. This operating technique may be effective, however if the feed
witnesses frequent variations in benzene level, this operating scheme will be nearly impossible.
For more effective operation and more profits, some refiners developed rigorous models for real
time optimization of penex process9. This shows the necessity of developing rigorous models in
modern refineries.
Another important variable is the H2:HC mole ratio inside the reactor. As indicated
before, hydrogen is required for completing isomerization and reducing coke lay-down on
catalyst. However, an increase in hydrogen partial pressure inside the reactors leads to an
increase in hydrocracking and reduction of isomerate yield. Therefore, the reactors should be
operated with the lowest possible hydrogen partial pressure. However, as a rule of thumb to
avoid coke deposition, the reactors should not be operated at H2:H.C ratio less than 0.05
measured at lag reactor outlet at any time.
Refiners face two operational scenarios in optimizing refinery processes. The first
scenario is "what-if" scenario where the refiners want to predict the process performance if a
change occurred to one or more of the process variables. This scenario has been covered in the
previous analysis of operating variables. The other scenario is the "how-to" scenario. Refiners
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usually aim at maximizing profits. Hence, the frequent question in refiners' minds is "How to
increase profit?"
In order to optimize the process, the notes obtained from the first scenario should be
implemented. Table 8 presents the base operating conditions of the investigated industrial unit
and the limit bounds induced by process licensor. It is clear that the reactors are operated with
H2:HC ratio much higher than required. Then, the first step was reducing hydrogen partial
pressure to the lowest possible value with the same reactors' inlet temperature. Actually, the
lowest possible H2:HC ratio at the reactors' outlet was 0.0865 which is still far from the
allowable minimum.
INSERT TABLE 8
Lower H2:HC ratios could be obtained but either at lower lead reactor temperature or
higher lag reactor inlet temperature because the amount of make-up hydrogen used affects heat
transfer coefficients in both the hot and cold combined exchangers and consequently affects the
outlet temperatures. Having obtained the lowest possible hydrogen partial pressure in reactors,
the next step was varying the lead and lag reactor inlet temperature simultaneously so as to
obtain the optimum operating point. Figures 17, 18 and 19 show the obtained results.
From Figure 17, the lower the reactors inlet temperatures, the higher the isomerate yield.
Therefore, it is always the refiner's decision to raise the reactors temperature to increase the
isomerization degree (Figure 18) to obtain a higher RON (Figure 19) with the sacrifice of
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isomerate yield. Table 9 shows a comparison between plant yields at base point and optimum
operating point.
INSERT FIGURE 17
INSERT FIGURE 18
INSERT FIGURE 19
INSERT TABLE 9
Results shown in Table 9 indicate that about 210 kg/hr can be added to the total regular
isomerate yield by following the optimization scheme. Savings in isomerate yield are mainly
attributed to decreased hydrocracking by reducing hydrogen partial pressure inside reactors. In
addition, it is shown that the reactor charge heater duty has declined due to reduced inlet
temperature of lead reactor and reduced load on heater by eliminating a part of make-up
hydrogen that was used originally. However, the decrease in reactor charge-heater duty is
overcome by the increase in stabilizer bottom reboiler, resulting in apparent energy deficiency of
about 96,635 kJ/hr. However, following the optimized operating scheme will not only improve
isomerate yield and RON, but it will also reduce the consumption of make-up gas. Make-up gas
from naphtha reformer may be directed to fuel gas system in the refinery. The new operating
scheme will add about 161 kg/hr of make-up gas to the fuel gas system. This will provide
approximately 11.3 x 106 kJ/hr. This may not only cover the increase in stabilizer bottom reboiler
duty, but also it may cover the total energy consumption of the fired heaters in the Penex unit. It
should be noted here that savings in energy and product yield are proportional to plant capacity.
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Finally, the model may be used to predict the plant performance at various operating
points. The model is extremely useful for predicting suitable operating conditions, especially
when plant experiences variations in feed benzene content. This can be achieved by
incorporating the model into a real time optimization (RTO) scheme. In this case, it is
recommended that the model be finely tuned to match plant performance closely.
7. Conclusions
A process model for an industrial Penex process was developed using Aspen HYSYS
Petroleum Refining isomerization reactor module. The model could track the plant performance
satisfactorily. In addition, the model was used for studying the effect of each process variable on
process performance. Among all process variables, benzene feed content and H2:HC ratio were
the most prominent factors to affect the process performance. Finally, the model was used for
optimizing process at steady state conditions. Results obtained from the model showed that
considerable savings in product yield can be achieved by lowering hydrogen partial pressure
inside reactors to the lowest possible practical value. The surplus in make-up gas may be directed
to fuel gas resulting in significant fuel savings. The model may also be incorporated in a real
time optimization (RTO) scheme. In this case, the model should be finely tuned to match plant
performance closely.
Nomenclature
A6
Benzene
C1
Methane
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C2
Ethane
C3
Propane
i-C4
Iso butane
n-C4
Normal butane
i-C5
Iso pentane
n-C5
Normal pentane
n-C6
Normal hexane
n-C7
Normal heptane
CH
Cyclo hexane
2,2-DMB
2,2 Dimethyl butane
2,3-DMB
2,3 Dimethyl butane
H factori
factor of component i
MCH
Methyl cyclo hexane
MCP
Methyl cyclopentane
MBP7
Multi branched heptanes
2MP
2-Methyl pentane
3MP
3-Methyl pentane
5N5
Cyclo pentane
5N7
Five ring, seven carbon naphthene
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6N7
Six ring, seven carbon naphthene
NP7
Normal heptane
SBP7
Single branched heptanes
7,-./
Temperature rise in reactor model
71/23
Temperature rise in plant reactor
Property of a petroleum fraction

Property of a pure component i

Mole , volume or mass fraction of component i
Known property of C7+ fraction

Weighting factor for component i
,-./0
Mass fraction of component i in model outlet stream
1/230
Mass fraction of component i in plant reactor outlet stream
PIN
Paraffin Isomerization Number = i-C5/C5 + (2,2-DMB+2,3-DMB)/C6
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Tables
Table 1: RON of normal and iso paraffins16,17

RON
Component
62
n-pentane
92
i-pentane
2-Methyl Pentane (2MP)
3-Methyl Pentane (3MP)
74.5
2,2 dimethyl butane (2,2-DMB)
91.8
2,3 dimethyl butane (2,3-DMB)
105.8
n-hexane
24.8
28
`
73.4
Page 29 of 56
Energy & Fuels
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Table 2: PNA composition of C7+ fraction

Hydrocarbon class
Vol.%
Paraffins
74.24
Naphthenes
23.53
Aromatics
2.22
29
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Energy & Fuels
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8
9
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35
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38
39
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41
42
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45
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48
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Page 30 of 56
Table 3: Available and calculated Properties of C7+ fraction in feed and product streams
Property
C7+ (Feed)
C7+ (Product)
Given
Calc.
Given
Calc.
SG
0.6915
0.7042
0.683
0.709
MW
100.198 99.666
100.198
99.70
RVP (psi)
1.97
1.97
2.1
2.187
RON
55
55
82
82
30
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Page 31 of 56
Energy & Fuels
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3
4
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7
8
9
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11
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13
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17
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19
20
21
22
23
24
25
26
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29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Table 4: Estimated composition of C7+ fraction in feed and product streams

Compnent
Feed (wt.%)
Product (wt.%)
MBP7
48.2
SBP7
52.7
27.3
N-C7
21.2
5N7
10.1
12.2
6N7
16
12.3
31
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Energy & Fuels
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5
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7
8
9
10
11
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14
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16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 32 of 56
Table 5: Adjustment factors used for reactor model calibration

Range of deviation
Parameter
from the base
Global activity
0.1-1
Isomerization activity
0.1-1.1
Hydrocracking activity
0.1-1.1
Hydrogenation activity
0.1-1.1
Ring opening activity
0.1-1.1
Heavy activity
0.1-1.1
32
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Page 33 of 56
Energy & Fuels
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2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Table 6: Terms included in objective function for reactor model calibration and applied
weighing factors
Term
Applied weighing factor
Temperature Rise (C)
I-Pentane (wt%)
N-Pentane (wt%)
Cyclo Pentane (wt%)
2 Methyl Pentane (wt%)
3 Methyl Pentane (wt%)
2,2 Di-Methyl Butane (wt%)
2,2 Di-Methyl Butane (wt%)
N-Hexane (wt%)
Methyl Cyclo Pentane (wt%)
Benzene (wt%)
Cyclo Hexane (wt%)
C7+ (wt%)
33
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Energy & Fuels
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7
8
9
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31
32
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39
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42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 34 of 56
Table 7: Estimated average activity parameters for lead and lag reactors
Parameter
Lead Reactor
Lag reactor
Global activity
0.912
2.402
Isomerization activity
0.827
1.092
Hydrocracking activity
1.023
0.968
Hydrogenation activity
0.939
0.995
Ring opening activity
1.054
1.042
Heavy activity
1.07
1.059
34
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Page 35 of 56
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
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52
53
54
55
56
57
58
59
60
Energy & Fuels
Table 8: Operating conditions of the unit at the base operating point and limit bounds induced by
process licensor
Process Variable
Base Operating Point
Bounds
H2:HC ratio
0.1565
min. 0.05
Lead Reactor Inlet T
124 C
105 - 204C
Lag Reactor Inlet T
120C
105 - 204C
35
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Energy & Fuels
1
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3
4
5
6
7
8
9
10
11
12
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15
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20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
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42
43
44
45
46
47
48
49
50
51
52
53
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59
60
Page 36 of 56
Table 9: Process performance at base and optimum operating point

Reactor
Lead
Lag
Make-up
Reactor
Reactor
Hydrogen
Inlet T
Inlet T
Flow
(C)
(C)
(kg/hr)
Stabilizer
Charge
Isomerate
Reboiler
Heater
Yield
PIN
Duty
Duty
(kg/hr)
(kJ/hr)
(kJ/hr)
Base
Operating
124
120
614.2
1,018,275
9,452,829
31,693
1.18
116
117
453
721,645
9,846,094
31,903
1.184
Point
Optimum
Operating
Point
36
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Page 37 of 56
Energy & Fuels
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31
32
33
34
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40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figures
Figure 1: Effect of temperature on isomers yield5
37
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Energy & Fuels
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46
47
48
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51
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53
54
55
56
57
58
59
60
Figure 2: Comparison of the activity of different isomerization catalysts5
38
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Page 38 of 56
Page 39 of 56
Energy & Fuels
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53
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57
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59
60
Figure 3: UOP Penex process6
39
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Energy & Fuels
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53
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55
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57
58
59
60
Figure 4: Isomerization model reaction network
40
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Page 40 of 56
Page 41 of 56
Energy & Fuels
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51
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53
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55
56
57
58
59
60
6
5
C7+ wt.%
4
3
2
1
0
25-Feb
16-Apr
5-Jun
25-Jul
13-Sep
Figure 5: Variation of C7+ wt% in the feed
41
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Energy & Fuels
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Page 42 of 56
40
35
i-C-5%
30
n-C5
5N5
Model (wt%)
25
2,2DMB
20
2,3
DMB
2MP
15
3MP
10
N-C6
5N6
5
0
0
10
15
20
25
Plant (wt.%)
30
35
40
Figure 6: Plant versus model yields with model calibration data sets forlead reactor
42
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Page 43 of 56
Energy & Fuels
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51
52
53
54
55
56
57
58
59
60
45
40
i-C-5%
35
n-C5
30
Model (wt%)
5N5
25
2,2DMB
20
2,3
DMB
2MP
15
3MP
10
N-C6
5N6
0
0
10
15
20
25
Plant (wt.%)
30
35
40
45
Figure 7: Plant versus model yields with model calibration data sets for lag reactor
43
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Energy & Fuels
40
35
i-C-5%
30
Model (wt%)
1
2
3
4
5
6
7
8
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Page 44 of 56
n-C5
5N5
25
2,2DMB
20
2,3
DMB
2MP
15
3MP
10
N-C6
5
5N6
0
0
10
15
20
25
30
35
40
Plant (wt%)
Figure 8: Plant versus model yields for the 4 months after calibration for lead reactor
44
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Page 45 of 56
Energy & Fuels
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47
48
49
50
51
52
53
54
55
56
57
58
59
60
40
35
i-C-5%
n-C5
30
5N5
Model (wt%)
25
2,2DMB
20
2,3
DMB
2MP
15
3MP
10
N-C6
5N6
5
0
0
10
15
20
25
Plant (wt%)
30
35
40
Figure 9: Plant versus model yields for the 4 months after calibration for lag reactor
45
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Energy & Fuels
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43
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49
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51
52
53
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57
58
59
60
Figure 10: Penex isomerization unit model
46
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Page 46 of 56
Page 47 of 56
(B)
(A)
74
73.8
(I-C5/C5)%
RON
84.15
84.14
84.13
84.12
84.11
84.1
84.09
84.08
84.07
84.06
73.6
73.4
73.2
73
72.8
105
110
115
120
Lead Reactor Inlet Temp. C
72.6
125
105
110
115
120
125
(D)
8.55
(2,3DMB/C6)%
(2,2DMB/C6)%
(C)
27.8
27.6
27.4
27.2
27
26.8
26.6
26.4
26.2
26
25.8
8.5
8.45
8.4
8.35
8.3
105
110
115
120
105
125
110
115
120
125
(E)
(F)
95.28
908
95.27
906
Isomerate wt.%
Hydrogen consumption
(STD_m3/hr)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
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46
47
48
49
50
51
52
53
54
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58
59
60
Energy & Fuels
904
902
900
898
896
95.26
95.25
95.24
95.23
95.22
95.21
95.2
95.19
894
892
105
110
115
120
95.18
125
105
110
115
120
125
Figure 11: A- Effect of Lead reactor inlet temperature on RON; B- Variation of (I-C5/C5)%
with lead reactor inlet temperature; C- Variation of (2,2DMB/C6)% with lead reactor inlet
temperature; D- Variation of (2,3DMB/C6)% with lead reactor inlet temperature; E- Effect of
lead inlet reactor temperature on hydrogen consumption in lead reactor; F- Effect of lead
reactor inlet temperature on isomerate yield. Lag reactor inlet temperature = 120 C, H2:HC =
0.1565, A6 = 2.99 wt.%, LHSV = 1.15 hr-1
47
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Energy & Fuels
(A)
(B)
84.12
76.5
84.1
76.45
RON
(I-C5/C5)%
84.14
76.55
84.08
84.06
76.4
76.35
84.04
76.3
84.02
76.25
106
111
116
121
Lag Reactor Inlet Temp. (C)
126
106
111
116
121
126
(D)
32.9
8.62
(2,3DMB/C6)%
32.8
(2,2DMB/C6)%
8.64
(C)
32.7
32.6
32.5
8.6
8.58
8.56
8.54
8.52
32.4
8.5
32.3
8.48
106
111
116
121
106
126
111
116
121
(E)
4
3.5
3
2.5
2
1.5
1
0.5
0
106
111
116
121
126
95.22
95.215
95.21
95.205
95.2
95.195
95.19
95.185
95.18
95.175
110
115
120
Figure 12: A- Effect of Lag reactor inlet temperature on RON; B- Variation of (I-C5/C5)%
with lag reactor inlet temperature; C- Variation of (2,2DMB/C6)% with lag reactor inlet
temperature; D- Variation of (2,3DMB/C6)% with lag reactor inlet temperature; E- Effect of
lead inlet reactor temperature on hydrogen consumption in lag reactor; F- Effect of lag
reactor inlet temperature on isomerate yield. Lead reactor inlet temperature = 124 C, H2:HC
= 0.1565, A6 = 2.99 wt%, LHSV = 1.15 hr-1
48
`
126
(F)
Isomerate wt.%
Hydrogen consumption
(STD_m3/hr)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
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Page 48 of 56
125
Page 49 of 56
(A)
96.4
Isomerate wt.%
96.2
96
95.8
95.6
95.4
95.2
95
0.07
0.09
0.11
0.13
0.15
0.17
H2:HC
RON
(B)
84.22
84.21
84.2
84.19
84.18
84.17
84.16
84.15
84.14
84.13
84.12
0.07
0.09
0.11
0.13
H2:HC
0.15
0.17
(C)
1.183
1.1825
1.182
PIN
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
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60
Energy & Fuels
1.1815
1.181
1.1805
1.18
1.1795
0.08
0.1
0.12
H2:HC
0.14
0.16
Figure 13: A- Effect of H2:HC ratio on isomerate yield; B- Effect of H2:HC ratio on RON of
isomerate; C- Effect of H2:HC ratio on PIN. Lead reactor inlet temperature = 124C, lag
reactor inlet temperature = 120 C, A6 = 2.99 wt%, LHSV = 1.15 hr-1
49
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Energy & Fuels
(A)
1.11
(B)
95.3
95.28
Isomerate wt.%
1.1
1.09
PIN
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
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Page 50 of 56
1.08
1.07
1.06
95.26
95.24
95.22
95.2
95.18
95.16
1.05
95.14
105
110
115
120
125
105
Lead Reactor inlet T

1.03 hr-1
1.15 hr-1
110
115
120
1.3 hr-1
1.03hr-1
1.15hr-1
1.3 hr-1
Figure 14: A- Effect of feed rate (LHSV) on PIN; B- Effect of feed rate (LHSV) on
isomerate yield. Lag reactor inlet temperature = 120 C, H2:HC = 0.1565, A6 = 2.99 wt%
50
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125
Lead Reactor T
Page 51 of 56
(A)
1.181
PIN
1.18
1.1795
1.179
0
2
4
6
8
Feed MCP content, wt% (base 4.08%)
0.5
1.5
(D)
84.18
84.17
84.16
84.15
84.14
84.13
84.12
84.11
84.1
84.09
0.5
1.5
Feed CH content, wt% (base 1.18%)
(E)
(F)
95.26
95.4
95.24
Isomerate wt.%
95.5
95.3
95.2
95.1
95.22
95.2
95.18
95.16
95.14
95
95.12
94.9
0
95.1
2
4
6
8
0.5
1
1.5
51
`
(C)
84.3
84.25
84.2
84.15
84.1
84.05
84
83.95
(B)
1.18015
1.1801
1.18005
1.18
1.17995
1.1799
1.17985
1.1798
1.17975
RON
RON
PIN
1.1805
Isomerate wt.%
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Energy & Fuels
Energy & Fuels
(H)
Total Hydrogen Consumption
(STD_m3/hr)
0
2
4
6
914
912
910
908
906
904
902
0
0.5
1
1.5
(I)
3.2
3
2.8
2.6
2.4
2.2
2
0
2.85
2.8
2.75
2.7
2.65
2.6
0
Feed MCP content, wt%(base 4.08%)
0.5
1
1.5
2
Figure 15: A- Effect of feed MCP content on PIN; B- Effect of feed CH content on PIN; CEffect of feed MCP content on RON; D- Effect of feed CH content on RON; E- Effect of
feed MCP content on isomerate yield; F- Effect of feed CH content on isomerate yield; GEffect of feed MCP content on total hydrogen consumption; H- Effect of feed CH content on
total hydrogen consumption; I:- Effect of feed MCP content on hydrogen consumption in the
lag reactor; J- Effect of feed CH content on hydrogen consumption in the lag reactor. Lead
reactor inlet temperature = 124 C, lag reactor Inlet temperature = 120C, LHSV = 1.15hr-1
52
`
(J)
Hydrogen Consumption in
lag reactor (STD_m3/hr)
Total Hydrogen Consumption

(STD_m3/hr)
(G)
930
925
920
915
910
905
900
895
890
Hydrogen Consumption in
lag reactor (STD_m3/hr)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 52 of 56
Temperature Rise in lead

reactor
(A)
25-Jun 14-Aug
3-Oct
(C)
84.25
84.2
84.15
84.1
84.05
84
83.95
83.9
83.85
(B)
45
40
35
30
25
20
15
10
5
0
(D)
1.1
1.095
1.09
1.085
1.08
1.075
1.07
1.065
1.06
Feed benzene, wt% (base 2,99%)
2
4
6
Feed benzene content, wt% (base 2.99%)
(E)
(F)
Hydrogen Consumption in lead
reactor (STD_m3/hr)
96
95.8
95.6
95.4
95.2
95
94.8
94.6
94.4
2
4
6
PIN
RON
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
26-Jan 17-Mar 6-May
Isomerate wt%
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Energy & Fuels
A6 wt%
Page 53 of 56
0
2
4
6
1600
1400
1200
1000
800
600
400
200
0
0
2
4
6
Figure 16: A- Variation of feed benzene content; B- Effect of feed benzene content on lead
reactor temperature rise; C- Effect of feed benzene content on isomerate RON; D- Effect of
Feed benzene content on PIN in the lead reactor; E- Effect of feed benzene content on
isomerate yield; F- Effect of feed benzene content on hydrogen consumption in lead reactor.
Lead reactor inlet temperature = 124 C, lag reactor inlet temperature = 120C, LHSV = 1.15
hr-1
53
`
Energy & Fuels
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 54 of 56
96.49
96.49-96.5
Isomerate wt %
96.47
96.47-96.49
96.45
96.45-96.47
96.43
96.43-96.45
96.41
96.41-96.43
96.39-96.41
96.39
96.37-96.39
96.37
117 115
Lead Reactor T, oC
113
111
109
107112
114
116
118
120
124
122
Lag reactor T, oC
Figure 17: Variation of isomerate yield with reactors inlet temperatures
54
`
Page 55 of 56
Energy & Fuels
PIN
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1.186
1.184-1.186
1.184
1.182-1.184
1.182
1.18-1.182
1.18
1.178-1.18
1.178
1.176-1.178
1.176
1.174-1.176
1.174
1.172-1.174
1.172
1.17-1.172
1.17
124
117
115
Lead Reactor Inlet T, oC
121
113
111
118
109
107
112
115
Lag Reactor Inlet T, oC
Figure 18: Variation of Paraffin Isomerization Number with reactors inlet temperatures
55
`
Energy & Fuels
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Page 56 of 56
84.24
84.22
84.24-84.25
84.22-84.24
84.2-84.22
84.18-84.2
84.16-84.18
84.14-84.16
84.12-84.14
84.1-84.12
84.08-84.1
RON
84.2
84.18
84.16
84.14
84.12
84.1
84.08
117
114
Lead reactor inlet T, oC
111
108
112
114
116
118
120
122
124
Lag reactor inlet T, oC
Figure 19: Variation of isomerate RON with reactors inlet temperatures
56
`

Predictive Modeling and Optimization For An Industrial Penex Isomerization Unit A Case Study

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Predictive Modeling and Optimization for an

Energy & Fuels

Predictive Modeling and Optimization for an Industrial Penex

Chemical Engineering Department, Faculty of Engineering, Cairo University

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attention to modeling isomerization reactions over chlorinated alumina catalysts.

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ACS Paragon Plus Environment

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Benzene Saturation. Benzene saturation to cyclohexane is a highly exothermic rapid

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Reaction Rate = Global activity Reaction-class Activity Heterogeneous

ACS Paragon Plus Environment

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ACS Paragon Plus Environment

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Properities of a petroleum fraction of known composition could be calculated from

Using this principle, an optimization algorithm can be used to estimate the

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ACS Paragon Plus Environment

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The weight of hydrogen in each stream could be calculated by:

 !"#$ $ %#& ' = &%% ( #  %#& '  

ACS Paragon Plus Environment

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B- Running the model:

f*+ = * *,-./0 1/230 +4 + + 57,-./ 71/23 8

ACS Paragon Plus Environment

Energy & Fuels

ACS Paragon Plus Environment

Energy & Fuels

ACS Paragon Plus Environment

Energy & Fuels

ACS Paragon Plus Environment

Energy & Fuels

ACS Paragon Plus Environment

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Hydrogen to hydrocarbon mole ratio. Hydrogen is required for completing the

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Feed composition. A) Methylcyclopentane and cyclohexane: Generally, cyclic

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ACS Paragon Plus Environment

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6. Model application to process optimization

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ACS Paragon Plus Environment

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ACS Paragon Plus Environment

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ACS Paragon Plus Environment

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!"#$ $ %#& ' = &%% ( # %#& '

f+ = *,-./0 1/230 +4 + + 57,-./ 71/23 8