Simulation and optimization of continuous catalytic naphtha reforming process Section D-Research Paper

SIMULATION, SENSITIVITY ANALYSIS AND OPTIMIZATION

OF AN INDUSTRIAL CONTINUOUS CATALYTIC NAPHTHA
REFORMING PROCESS

Sepehr Sadighi[a] and S. Reza Seif Mohaddecy[a]*

Keywords: Catalytic Reformer, Simulation, Petro-Sim, Sensitivity Analysis, Optimization

Continuous catalytic regeneration (CCR) is a key process in petroleum refineries to produce high octane gasoline. In this article, a
commercial scale CCR plant with the nominal capacity of 22000 bbl day-1 was simulated using Ref-sim module and Petro-sim simulator.
The validity of this plant wide simulator was evaluated by actual test runs obtained during 6 months of operation. Simulation results
showed that the AAD % of momentous output variables i.e. outlet temperature of reactors, product volume yield, product RON, H2 purity
of recycle gas and coke deposition on the catalyst against actual data were 0.5 %, 0.94 %, 1.098 %, 0.57 % and 0.347 %, respectively.
Then, the optimal values for reactor temperatures, feed flow rate and recycle flow rate were determined using sensitivity analysis approach.
After setting these decision variables on the proposed optimal values, the actual RON and volume yield of the CCR plant enhanced from
99.55 and 82.04 % to 99.67 and 82.4 %, respectively.

Corresponding Authors recycled. The catalyst circulation and regeneration are

E-Mail: Seifsr @ripi.ir performed on a continuous basis with full automatic control.
[a] Catalysis and Nanotechnology Division, Catalytic Reaction
Engineering Department, Research Institute of Petroleum Continuous regeneration eliminates the need of shutdown
Industry (RIPI), [email protected] for regeneration of the earlier fixed bed reformers.
Additionally, it minimizes the amount of catalyst in the unit,
while allowing high gasoline yield and quality.4,5 The
Introduction variables that affect the efficiency of a CCR process are the
volume flow of naphtha feed, reactor inlet temperature,
The main objective of the catalytic reforming process is to hydrogen-to-oil molar ratio and temperature of the
enhance the octane number of the feed, mainly heavy separator. 6
naphtha. The need to increase the antiknock quality of
naphtha as a blending stock for motor fuels is the greatest In this research, after simulating a commercial CCR plant
single reason for installing catalytic reforming units.1 A using Petro-sim simulator (KBC, 2009), the effect of
large number of reactions occur in catalytic reforming, such process variables on the yield of reforming and RON of the
as dehydrogenation and dehydroisomerization of naphthenes product is discussed. Then, the optimal process variables
to aromatics, dehydrogenation of paraffins to olefins, were determined using the sensitivity analysis approach.
dehydrocyclization of paraffins and olefins to aromatics,
isomerization or hydroisomerization to isoparaffins,
isomerization of alkylcyclopentanes and substituted Process Description
aromatics, and hydrocracking of paraffins and naphthenes to
lower hydrocarbons.2 Some of these reactions are desired A commercial CCR unit, called Platformer licensed by
because of increasing octane number of gasoline and also UOP cooperation with the nominal capacity of 22000 barrel
purity of the produced hydrogen, and some of them are per day was chosen as a case study. The block flow diagram
undesired due to decreasing them. For instance, cyclization of the process is shown in Fig. 1. The feed of the plant prior
and aromatization reactions increase the octane number. to entering reactors should undergo hydro desulphurization
They are thus favorite ones. In contrast, coke formation and (HDS) reaction in the hydrotreatment unit. Then, the treated
coke deposition reactions cause the deactivation of the feed (Reformate) is passed through filters to remove any
catalyst; consequently, they are undesired reactions. particulate matter which may deposit on the welded plates
exchanger. The specifications of the feed are presented in
From the view of the operation, there are three kinds of Table 1. This feed is mixed with the recycle gas from the
relevant catalytic reforming units: 1. Semi-regenerative; 2. recycle compressor, and preheated against the fourth reactor
Continuously catalyst regenerative (CCR), and 3. Cyclic1, 2. effluent. Before entering to the catalytic reactors, it should
be heated to reach the reaction temperature above 500°C.
The CCR process consists of three or four adiabatic The reactors are radial flow types, so the feed flows through
reactors in series with intermediate heaters.2 Low octane the catalyst bed from the outer circumference towards the
hydrocarbons, such as paraffin’s and naphthenes are center pipe. In the first reactor, the reactions are
converted to high octane aromatics, hydrogen and other light predominantly endothermic; therefore, the reactor effluent
gases through this process.3 In a CCR plant, the reforming requires reheating in the first inter-heater to the required
reactions take place in a moving bed catalytic reactor from inlet temperature of second reactor. The reactions in the
which the catalyst is withdrawn; then it is regenerated and second reactor are less endothermic, but still require

Eur. Chem. Bull., 2013, 2(10), ppp-ppp 777

Simulation and optimization of continuous catalytic naphtha reforming process Section D-Research Paper

reheating in other heater before entering the third reactor. A portion of the separated gas is compressed by a recycle
The third reactor effluent is reheated in the third inter-heater gas compressor; then, it is recycled to the reactors. Finally,
before entering the fourth reactor. The effluent leaves the the liquid product leaving the separator is introduced to the
fourth reactor at approximately 468-486 °C (depending on gasoline stabilizer in which the LPG and light gases are
position in the cycle) and 3.3 bar. separated from the gasoline to set the vapour pressure of the
gasoline according to the market requirement. The
distribution of catalyst between reforming reactors in the
CCR plant studied in this work is shown in Table 2.
Moreover, the normal operating conditions prevailing in this
unit are presented in Table 3.

Table 2. Catalyst distribution in reforming reactors studied

First Second Third Fourth
Catalyst
Reactor Reactor Reactor Reactor

Weight (kg) 5880 6754 10545 18984

Distribution (wt %) 14 16 25 45

Figure 1. Block flow diagram of the continuous catalytic Table 3. Operating conditions in the CCR plant studied
reforming unit 7
Process variable Value
In all reforming reactors the feed contacts with the
reforming catalyst distributed approximately at the ratio of Inlet temperature (°C) 500 - 515
15/20/25/40 %. In the continuous regeneration process the Hydrogen/hydrocarbon ratio (mol mol-1)
catalyst circulates continuously: 3-7
LHSV (h-1) 1- 2
 In the reactors.
Yield (vol %) 70 - 85
 From one reactor bottom to the top of the next one.
 From the last reactor to the regeneration unit for
regeneration.
 From the regeneration unit, the regenerated catalyst Process Simulation
returns to the first reactor.
Catalytic reforming process is often modeled and
In the regeneration unit, catalyst circulation is achieved simulated based on the: 1. Number of reactive species, and
either by gravity flow or by gas lift systems. In order to 2. Type of the used kinetic model.8,9,10 Moreover, presence
obtaining a good regeneration of the spent catalyst, of many components as reactants or intermediate products in
operations such as coke burning, catalyst oxychlorination, the reactive mixture makes a sophisticated situation for
catalyst calcinations, catalyst cooling and catalyst reduction modeling and simulating the process. To decrease these
must be carried out. Leaving fourth reactor, the effluent after complications, reactants in the mixture are classified in
heat exchange against reactor feed, is cooled by air and certain and limited groups, called pseudo components. The
water exchange, respectively before entering the separator number of selected pseudo components in the mixture is a
drum. determinant factor interested in designed models.
Additionally, Arhenius and Langmuir–Hinshelwood kinetics
are widely used for kinetic-based catalyst modeling and
simulating of the catalytic naphtha reforming process11,12.
Table 1. Feed specifications of the CCR plant studied Petro-sim simulator, developed by KBC, is capable to
Distillation Case1 Case2 Case3 Case4
simulate industrial scale of catalytic reforming units.13 This
simulator can also simulate the catalytic reforming plants
Feb. 2011 April 2011 May 2011 July 2011
with three or four reactors; so, it enables us to simulate
Method (D86)
reactors with different catalyst weights and different
IBP °C 95 92 92 93 sizes.14,15 In this research, Petro-sim has been used to
10 % vol °C 107 104 104 104 simulate and analysis of the CCR plant studied.
30% vol °C 112 111 109 111
To simulate the catalytic naphtha reforming process using
50 % vol °C 118 117 114 117 Petro-sim, external calibration in order to determining the
70 % vol °C 126 127 125 125 kinetic parameters is essentially needed. For this unit, Ref-
sim module is applied to provide these factors15,16. It should
90 % vol °C 139 140 137 138 be mentioned that for generating these parameters i.e.
FBP °C 161 164 161 159 frequency factors, activation energies and decay constants,
PONA Analysis actual test runs from the under study unit should be
Naphthenes vol % 33.2 33.8 33.8 -
gathered. These parameters mainly consist of inlet and outlet
reactor temperatures, catalyst weight, specification of feed
Aromatics vol % 12.2 12.4 11.8 - and products, operating pressures, flow rates of makeup
Density kgm-3 746.5 745 745 744 hydrogen, recycle rates and flow rates of all gaseous and

Eur. Chem. Bull., 2013, 2(10), 777-781 778

Simulation and optimization of continuous catalytic naphtha reforming process Section D-Research Paper

liquid products. After preparing test runs and running Ref-

sim module, calibration factors are sent to the Petro-sim
environment in order to simulating and optimizing the under
study plant. The algorithm to tune and simulate CCR
process studied in this research is shown in Fig. 2.

Figure 3. Wide simulation of CCR plant studied

After validating the CCR simulator, it was applied to

sensitivity analysis of RON and yield of the produced
gasoline. Fig. 4 and Fig. 5 show the sensitivities of RON
and volume yield of the gasoline (or Reformate) to the
Figure 2. Algorithm of tuning and the CCR plant using Ref-sim temperature of reactors in the CCR plant studied.
module

Results and discussions

Actual test runs were gathered from the CCR unit

described in the earlier sections. The data used for the
calibration should be selected from the normal condition
when no abnormalities, such as tower flooding, emergency
depressurization and pump or compressor shut down were
happen in the operation. Before using these data to estimate
the tuning parameters, it was necessary to validate them. If a
reasonable overall mass balance (±5%) cannot be calculated,
the validity of test run was compromised. Additionally, from
Table 1, it was found that the variation in feed specification
was not considerable, and its effect on the yield and RON of Figure 4. Effect of reactors inlet temperature on product RON
the CCR plant can be ignored. The calibration parameters
were then generated by Ref-sim module, and they were
exported to the Petro-sim simulator to create the wide
simulator of the CCR plant studied. The flow sheet of CCR
wide simulator developed in Petro-sim environment is
shown in Fig. 3. To evaluate and validate the simulation, the
significant simulated variables i.e. outlet temperature of 1st,
2nd, 3rd, and 4th reactors, product volume yield, product
RON, H2 purity in recycle gas and coke deposition on the
catalyst were compared against the actual data points.

Comparison of these momentous process variables for

four data sets obtained during 6 months of study are shown
in Tables 4 and 5. From these tables, it can be concluded
that the average AAD % of the calculated outlet
temperatures using the CCR simulator was less than 0.5 %
for all data sets. In addition, the AAD % of simulation for
yield, RON of product, H2 purity in recycle gas and coke Figure 5. Effect of reactors inlet temperature on product volume
deposition on catalyst were 0.94 %, 1.098 %, 0.57 % and yield
0.347 %, respectively.
As observed in Figures 4 and 5, the RON of product was
From the AAD% of the simulation, the validity of wide enhanced by increasing the temperature of reforming
simulator was confirmed during 6 months of operation; reactors. In contrast, the yield of the gasoline dropped by
therefore, it is reliable to study the under study CCR plant. increasing the temperature.

Eur. Chem. Bull., 2013, 2(10), 777-781 779

Simulation and optimization of continuous catalytic naphtha reforming process Section D-Research Paper

Table 4. Comparison of outlet temperature of 1st to 4th reactors of the CCR plant studie
Variable Unit Test run 1 Test run 2 Test run 3 Test run 4 AAD %
A S A S A S A S
1st reactor °C 393.1 395.1 395.8 397.0 393 392 396.7 394.3 0.417
2nd reactor °C 446.1 444.2 448.35 448.3 445.9 446.3 448.7 449.9 0.197
3rd reactor °C 464.3 461.6 465.8 462.1 464.4 465.3 465.6 465.6 0.396
4th reactor °C 480.8 476.65 480.9 475.8 479.9 479.7 480.9 479.6 0.558
A: Actual, S: Simulation, AAD: Absolute Average Deviation

Table 5. Comparison of product yield, product RON, hydrogen purity in recycle gas and coke on catalyst of the CCR plant studied
Variable Unit Test run 1 Test run 2 Test run 3 Test run 4
AAD%
A S A S A S A S
Yield vol % 84.48 83.8 81.59 81.76 81.5 82.29 81.69 82.51 0.94
RON - 99.1 97.54 98.73 97.44 98.88 98.1 98.8 98.14 1.087
H2 purity mole % 89.27 89.49 88.48 88.87 88.3 88.95 88.37 89.13 0.57
Coke wt %/ 4.5 4.48 5.6 5.57 4.3 4.29 4.5 4.48 0.347

It may be supposed that the hydrocracking reactions are product yield. According to this figure, optimal feed flow
promoted more than the cyclization of paraffins, in rate of 148 m3 h-1 is determined. As illustrated by the (▲)
consequence with increasing RON of the product, and points in Figs.7, increasing the recycle flow rate
also decreasing the volume yield. From Fig. 5, the decreases the yield of the process (left y-axis), but the
optimum inlet temperature for all reactors is determined right y-axis and (●) points show that increasing this
about 515 °C. decision variable increases RON of the reformate. In fact,
increasing the recycle flow rate elevates H2 to
hydrocarbon ratio; therefore, hydrocraking reactions are
The effects of feed (heavy naphtha) and recycle flow strongly promoted. Enhancing hydrocracking reactions in
rates on the RON and volume yield of gasoline are shown reforming reactors increases RON of product, and
in Figw. 6 and 7. In these figures, for all cases, the left y- decreases product volume yield. According to this figure,
axis and (▲) points show the volume yield and the right optimal recycle flow rate of 45000 m3 h-1 can be
y-axis and (●) points show the RON of the product. determined.

Figure 6. Effect of feed flow rate on product RON and volume Figure 7. Effect of recycle flow rate on product RON and
yield volume yield

As illustrated by the (▲) points in Fig.6, by increasing

the feed flow rate, the yield of the process (left y-axis)
increases, but the right y-axis and (●) points show that Finally, to evaluate the optimal determined point for the
increasing the feed flow rate drops the RON of the CCR plant, reactor temperature of all reactors, feed flow
reformate. Since the inverse of the feed flow rate divided rate and recycle flow rate were manipulated from
by the amount of catalyst is linked with the residence 512.9°C, 150 m3 h-1 and 45400 m3 h-1 to the estimated
time of the reactor, it affects directly the kinetic of the optimal point i.e. 515°C, 148 m3 h-1 and 45000 m3 h-1,
reforming reactions. Decreasing the feed flow rate respectively. It was observed that the actual RON and
increases residence time in consequence with higher volume yield of the CCR plant were enhanced from 99.55
severity, hence it increases product RON, and decreases and 82.04 % to 99.67 and 82.4 %, respectively.

Eur. Chem. Bull., 2013, 2(10), 777-781 780

Simulation and optimization of continuous catalytic naphtha reforming process Section D-Research Paper

3
Conclusion Ancheyta J., Villafuerte E., Energy Fuels, 2000, 14, 1032-
1037.
4
In this work, a commercial scale continuous catalytic Gyngazova M. S., Kravtsov A. V., Ivanchina E. D., Korolenko
reformer, a key process for producing high octane M. V., Nikita V., Chem. Eng. J., 2011, 176–177, 134–143.
gasoline, was simulated. Operating data was obtained 5
Weifeng H., Hongye S., Shengjing M., Jian C., Chin. J. Chem.
from a commercial scale CCR plant for calibrating the Eng., 2007, 15(1), 75-80
simulator using Ref-sim module; then, the wide simulator 6
Sa'idi M., Mostoufi N., Sotudeh R., Int. J. Appl. Eng. Res.,
of CCR unit was created in Petro-sim environment. 2011, 2(1),115-124.
Results showed that for four data sets gathered during 6 7
Weifeng H., Hongye S., Yongyou H., Jian C., Chin. J. Chem.
months of study, the average AAD % of the simulated Eng., 2006, 14(5), 584-591.
outlet temperatures, volume yield, RON of product, H2 8
purity and coke deposition on the catalyst against actual Shakoor Z. M., Diyala J. Eng. Sci., 2011, 4(2), 86-104.
9
data were about 0.5 %, 0.94 %, 1.098 %, 0.57 % and Arani1 H. M., Shirvani M., Safdarian K., Dorostkar E., Braz.
0.347 %, respectively. J. Chem. Eng., 2009, 26(4), 723–732.
10
Mohaddeci, S. R., Sadighi, S., Zahedi, S., Bonyad, H., Petrol.
After validating the simulation, sensitivity analysis Coil, 2006, 48(3), 28-35.
showed that the RON of product increased by elevating 11
Mohadesi M., Mousavi H.S., Chem. Prod. Process Model.,
the temperature of the reactors, but the yield of the 2012, 7, 1-25.
gasoline dropped. Moreover, it was found that increasing 12
Arani H. M., Shokri S., Shirvani M., Int. J. Chem. Eng. Appl.,
the feed flow rate increased the yield of the process, but 2010, 1(2), 159-164.
the RON of the gasoline decreased by increasing that. In 13
contrast, increasing recycle flow rate increased the Petro-Sim User Guide, KBC Advanced Technologies, KBC
Profimatic, 2012
product RON, but it decreased the volume yield.
14
Ke-min, L., Hai-yan, G., Shie-wei, P., J. Zhejiang Univ. Sci.,
According to this analysis, the optimal inlet 2005, 590-596.
15
temperature for all reactors, feed and recycle flow rates Seif Mohaddecy S. R., Sadighi S., Bahmani M., Petrol. Coal
were 515°C, 148 m3 h-1 and 45000 m3 h-1, respectively. J., 2008, 50(2), 60-68.
After setting the process variables on these optimal 16Askary A., Karimi H., Rahimi M. R., Farayandno J. Natl.
values, it was observed that the actual volume yield and Iranian Refining, 2012(37), 39-55
RON of gasoline increased to 99.67 and 82.4 %,
respectively. Therefore the efficacy of the presented
optimization approach was confirmed.

References
1
Antos G.J., Aitani A.M., Catalytic Naphtha Reforming, CRC
Press, New York, USA, Feb 1, 2004
2
Zahedi G., Mohammadzadeh S., Moradi G., Energy Fuels, Received: 27.04.2013.
2008, 22, 2671–2677. Accepted: 23.05.2013.

Eur. Chem. Bull., 2013, 2(10), 777-781 781