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Optimization of Operating Parameters of Continuous Catalytic Naphtha

Reforming Process using Response Surface Methodology

Conference Paper · November 2011

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 7th International Chemical Engineering Congress & Exhibition
Kish, Iran, 21-24 November, 2011

Optimization of Operating Parameters of Continuous Catalytic

Naphtha Reforming Process using Response Surface Methodology

Behnam Taghaviα , Shohreh Fatemiα*, Seyed Mojtaba Razaviβ

α
Department of Chemical Engineering, Faculty of Engineering,University of Tehran, Tehran, Iran
β
Bandar Abbas Oil Refining Co., Bandar Abbas, Iran
*
shfatemi@ut.ac.ir

Abstract
Optimization of the operating parameters of continuous catalytic naphtha reforming process
including temperature, pressure and hydrogen to hydrocarbon ratio was conducted using a
response surface methodology for a unit with three or four beds to achieve to the highest reformate
yield and research octane number (RON). The results were analysed by Analysis of Variance
(ANOVA) to realize the significant effect of the operational parameters and their interactions on
the reformate yield and RON. Taking 95% confidence level into account, each factor with a
significant level of lower than 5% can be regarded as a significant factor. The ANOVA was
performed with the help of statistical software, Design Expert 8. It was concluded that using three
reactors instead of four, required around 17k increase in the inlet temperature of the reactors to
approach to the same industrial target of RON and yield of reformate.

Keywords: Optimization, Catalytic naphtha reforming, Moving bed, Radial flow reactor

Introduction
Catalytic naphtha reforming is one of the key processes in petroleum refining for octane
improvement and production of aromatic feedstock for petrochemical industries. Hydrogen is
a valuable byproduct of naphtha reforming process and in most refineries it is the source of
part or all of the hydrogen used for hydrocracking, hydrotreating, and other hydrogen-
consuming processes [1-3]. Although CCR plants have become increasingly important, most
of the published works are focused on modeling and simulation of the semiregenerative
naphtha reformers [4-10].
In our previous work [11], modeling and simulation of the commercial CCR in the radial
moving beds was developed. After evaluation and validation of the model, optimization of the
operational conditions and finding an optimal number of reactors is the ultimate scope of
simulation that is taken place by the response surface methodology to achieve the highest
yield of reformate and RON consistent with the industrial CCR unit in Bandar Abbas
Refinery.
Optimization of Operating Parameters of Continuous Catalytic Naphtha ……

Kinetic Model
In the present model, the naphtha feed and reforming products are considered as twenty-six
hydrocarbon lumps which characterized by naphthenes (alkyl cyclohexanes(ACH) and alkyl
cyclopentanes (ACP)), normal paraffins (NP), isoparaffins (IP), and aromatic (A) lumps with
carbon number ranging from C6-C9 [7]. There are 12 sets of reactions in present model such as
dehydrogenation and dehydroisomerization of naphthenes to aromatics, dehydrogenation of
paraffins, dehydrocyclization of paraffins to aromatics, isomerization or hydroisomerization to
isoparaffins, isomerization of alkylcyclopentanes, and substituted aromatics and
hydrocracking of paraffins and naphthenes to lower hydrocarbons. A generalized reaction
scheme that identifies as key reactions and the reaction pathways that are required to achieve
high product yields, are depicted in Figure 1 [12].

Figure 1: A generalized naphtha reforming reaction scheme [12]

The continuous reforming process developed in Bandar Abbas Refinery uses four stacked
radial-flow reactors and a CCR section to maintain a steady-state reforming operation at
optimal process conditions: fresh catalyst performance, low reactor pressure, and minimum
recycle gas circulation. The basic flow pattern through the platforming unit with CCR is
essentially the same as with conventional fixed bed units, where catalyst is transported
through the reactors by gravity [1-3,12]. The internal and external mass transfer resistances
are ignored in the mole balance and energy balances equations because of the previous
researches [10]. For a radial-flow reactor, the global material and heat balance equations can
be defined by equations 1 and 2, respectively. The activity functions and the rate of coke
formation are presented in equations 3 [13].

dFi
 (2RL  b ) ri (1)
dR

9
 12 
   (H in )rin 
 (2 RL b ) n 6  i 1 
dT
(2)
dR  j j
F Cp

 i C
ri  ri0i , 0  i  1 Where i  e (3)
 7th International Chemical Engineering Congress & Exhibition
Kish, Iran, 21-24 November, 2011

Optimization
Considering the results of the CCR simulation, it is revealed that the composition profiles and
temperature along the fourth bed of CCR is not apparently significant, therefore it is decided
to determine the optimal operational conditions to approach to the highest efficiency of the
process either using a four-bed CCR or a three-bed one. The present validated model was used
in order to determine the reformate yield and RON at various operational parameters. The
effect of variation of the operating parameters such as temperature, pressure and input
hydrogen to hydrocarbon ratio as well as the number of reactors were investigated by a
Response Surface Methodology based on statistical analysis to determine the optimal
conditions and admit the industrial restrictions. The range and level of the studied parameters
are shown in Table 1. A central composite design with 30 test runs was applied and two
responses (reformate yield and RON) were derived from the model [14]. The results were
analysed by Analysis of Variance (ANOVA) to realize the significant effect of the operational
parameters and their interactions on the reformate yield and RON. The ANOVA was
performed with the help of statistical software, Design Expert 8.

Table 1: variable Ranges for the operating condition

Parameter Lower Center Upper

Temperature(◦C) 490 510 530

Pressure (Bar) 5 7 9
H2/HC (mol/mol) 2.4 2.7 3
No. Reactor 3 - 4

Results and Discussion

The model integrates numerically the component and energy balance differential equations by
fourth order Runge-Kutta method for each individual reactor.
The 30 different runs are presented in the Table 2 with their two responses derive from the
CCR model. To investigate the effect of each parameter and their interactions on the output
responses (yield and RON), Ficsher values (F-value) were calculated by the ratio of variance
of the response for each factor over the variance of the residuals (MSSParameter/MSSResidual)
[14]. The calculated F- Values of each factor are presented in Figures 2 and 3 for RON and
yield, respectively. The higher the F-value of any parameter reveals the more significant effect
of that parameter on the response. The significance of each parameter can be utilized by the
probability value (P-value) that is a measure of significant level calculated from the F-value.
Taking 95% confidence level into account, each factor with a significant level of lower than
5% can be regarded as a significant factor. The order of significancy of each factor can be
seen by the Ficsher values (F-value) in Figure 2 and 3 for RON and yield, respectively.
It is concluded that temperature, reactors no., pressure and binary interactions consisting T-
reactor no., P- reactor no. and T-P have respectively the most significant effect on RON. Also
the effect of temperature, reactor no., T-reactor no., T-P, pressure, H2/HC ratio, P-reactor no.
and T-H2/HC are respectively the most effective parameters for the yield of reformate. The
numerical results of the ANOVA calculations are shown in Table 3.
Optimization of Operating Parameters of Continuous Catalytic Naphtha ……

In Table 3, Estimated coefficients reveal the positive and negative effects of the significant
parameters. Temperature, reactors no., and pressure induce the positive effects on RON, that
mean increasing these parameters causes enhancement of RON,whereas rising temperatures,
reactors no. and H2/HC ratio induce the negative effect on reformate yield, that means
reduction of these parameters would reduce the yield of reformate. Also the positive and
negative effect of binary interactions of this parameters is presented in Table 3.
For better understanding the effect of operating parameters on the results of CCR simulation,
the effect of some important parameters are presented, graphically, resulted from statistical
analysis. The effects of temperature and pressure on oactane number are shown in figures 4
and 5 using three or four beds.

Table 2: 30 different runs as function of temperature, pressure, H2/HC and reactor No. with the resulted
responses of RON and Reformate yield
Factor 4 ; D:Reactor No.

Factor 4 ; D:Reactor No.

Factor 3 ; C:H2/HC

Factor 3 ; C:H2/HC
Response 2 ; Yield

Response 2 ; Yield
Response 1 ; RON

Response 1 ; RON
Factor 2 ; B:P

Factor 2 ; B:P
Factor 1 ; A:T

Factor 1 ; A:T
Run

Run

1 490 5 2.4 R3 78.08 91.35 16 490 5 2.4 R4 82.76 88.6

2 530 5 2.4 R3 95.5 77.23 17 530 5 2.4 R4 108.4 69.06

3 490 9 2.4 R3 82.4 91.03 18 490 9 2.4 R4 90.71 87.73

4 530 9 2.4 R3 101.03 80 19 530 9 2.4 R4 113.61 73

5 490 5 3 R3 78.12 91.28 20 490 5 3 R4 82.86 88.5

6 530 5 3 R3 95.88 76.77 21 530 5 3 R4 108.7 68.66

7 490 9 3 R3 82.2 91.02 22 490 9 3 R4 90.44 87.73

8 530 9 3 R3 101.15 79.63 23 530 9 3 R4 113.64 72.67

9 490 7 2.7 R3 80.46 91.15 24 490 7 2.7 R4 87.6 87.86

10 530 7 2.7 R3 99.41 78.51 25 530 7 2.7 R4 112.25 71.02

11 510 5 2.7 R3 84.15 86.41 26 510 5 2.7 R4 93.72 80.58

12 510 9 2.7 R3 90.18 86.75 27 510 9 2.7 R4 102.05 81.28

13 510 7 2.4 R3 88.01 86.51 28 510 7 2.4 R4 99.3 80.78

14 510 7 3 R3 88 86.36 29 510 7 3 R4 99.29 80.6

15 510 7 2.7 R3 88.02 86.43 30 510 7 2.7 R4 99.31 80.67

 7th International Chemical Engineering Congress & Exhibition
Kish, Iran, 21-24 November, 2011

Figure 2: F Value of effective parameters for RON

Figure 3: F Value of effective parameters for reformate yield

Optimization of Operating Parameters of Continuous Catalytic Naphtha ……

Table 3: Analysis of variance with 95% confidence level

RON Reformate Yield

Coefficient Mean F p-value Coefficient Mean F p-value

Source df Source df
Estimate Square Value Prob > F Estimate Square Value Prob > F

Model 11 300.6558 5555.559 < 0.0001 Model 15 93.88782 21294.16 < 0.0001

A-T 10.697 1 2288.516 42287.51 < 0.0001 A-T -7.37 1 217.2676 49277.23 < 0.0001

B-P 3.59 1 51.5524 952.5922 < 0.0001 B-P 0.26 1 0.2704 61.32789 < 0.0001

D-Reactor -0.1035
5.531 1 305.9196 5652.824 < 0.0001 C-H2/HC 1 0.214245 48.59169 < 0.0001
No.

AB -0.18625 1 0.555025 10.25583 0.0049 D-Reactor No. -2.855 1 81.51025 18486.88 < 0.0001

AD 1.526 1 46.57352 860.5918 < 0.0001 AB 0.9875 1 15.6025 3538.714 < 0.0001

BD 0.439 1 3.85442 71.22249 < 0.0001 AC -0.08625 1 0.119025 26.99538 0.0001

A 2
1.442143 1 11.64675 215.2101 < 0.0001 AD -1.116 1 24.90912 5649.496 < 0.0001

B 2
-0.96286 1 5.191726 95.93341 < 0.0001 BD 0.081 1 0.13122 29.76126 < 0.0001

ABD -0.48625 1 3.783025 69.90325 < 0.0001 A2 -1.50889 1 11.70898 2655.647 < 0.0001

A2B -0.785 1 1.97192 36.4374 < 0.0001 B2 0.111111 1 0.063492 14.40027 0.0020

2
AD -0.694 1 3.210907 59.33157 < 0.0001 C 2 -0.08139 1 0.034067 7.726557 0.0148

Residual 18 0.054118 ABD 0.21125 1 0.714025 161.9439 < 0.0001

R-Squared=0.9997 A2B 0.45 1 0.648 146.9692 < 0.0001

2
AD 0.198 1 0.26136 59.27757 < 0.0001

AB 2 -0.14375 1 0.066125 14.99743 0.0017

Residual 14 0.004409

R-Squared=1.0000

Figure 4: The effect of temperature on RON for three and four beds
 7th International Chemical Engineering Congress & Exhibition
Kish, Iran, 21-24 November, 2011

Figure 5: The effect of pressure on RON for three and four beds

Figure 6: The effect of temperature on reformate yield for three and four beds

From figures 4 and 5, it is concluded that the use of four reactors would result to the higher
RON. The higher the temperature the enhancement of RON is observed due to the accelerated
reaction of aromatic production. In addition, the higher the pressure the more improvement of
RON is observed because of more hydrocracking of paraffines and isoparafins.
Figure 6 represents the effect of temperature on the yield of reformate, that firstly shows three
number of reactors would cause more liquid reformate production. In addition higher
temperatures results lower yield of liquid reformate. Using four reactor and/or higher
Optimization of Operating Parameters of Continuous Catalytic Naphtha ……

operating temperature would cause more decomposition of the feed to the LPG, therefore
reduces the yield of liquid product. In addition, the results of Table 3 show the significant
effect of pressure and H2/HC ratio on the yield of reformate. In this table, the columns of
coefficients represent the quadratic model for RON and liquid yield versus temperature,
pressure, H2/HC and reactor No.
According to the effective operational parameters, opposite results are arised between RON
and yield of reformate. As mentioned before temperature rise improves RON but yield, and
application of four reactors enhances RON but decreases the yield. Also the ratio of H2/HC
has a significant negative impact on the yield with no impact on RON. Therfore optimization
of operational parameters is required to maximize RON and achieve to the highest possible
yield efficiency. The quadratic models of RON and yield derived from response surface
methodology were used in the simplex optimization method to determine the optimal
conditions of temperature, pressure, H2/HC ratio and No. of reactors. The ranges of studied
parameters were restricted within allowed industrial conditions, in which temperature was
stuied from 490 to 530 ◦C pressure from 5 to 7 bar and H2/HC ratio from 2.5 to 2.9 with three
or four reactors. Various conditions met the desired level of responses. The best conditions are
summerized in Table 4. In this table two cases are compared with each other, working with
four or three reactors. Case I which is closer to the current industrial conditions suggests
working at pressure of 7 bar , inlet temperature of 507.4 ◦C, H2/HC of 2.53 with four reactors
to achieve 97.6 RON and 81.8% yield, respectively. To reduce the No. of reactors for catalyst
saving, Case II should be replaced, whereas it requires higher inlet temperature of 524.5 ◦C to
approach to nearly the same RON and yield.
On the other hand two last cases are proposed for working at 9bar pressure. In Case III, the
required inlet temperature is 502.7◦C which is 5 degree lower than the Case I and 2% higher in
the reformate yield. Case IV, has similar conditions of Case II although working at 9 bar and
only two unit improvement in RON is observed, therefor it is concluded that pressure
improvement is not required in presence of high temperatures.

Table 4: Optimum operating conditions

Case P, bar T,C H2/HC No. Reactor RON Yield (%) Desirability

I 507.54 2.53 R4 97.62 81.82 0.83

7
II 524.47 2.4 R3 95.8 81.15 0.78

III 502.76 2.57 R4 98 83.81 0.82

9
IV 524.81 2.4 R3 98 82.01 0.76

At P=7 bar, desired parameters have not changed dramatically, so it can be said that for the
establishment of the new plants it is more desirable to construct a CCR with three reactor, and
working at higher level of inlet temperature, although for stability of the catalyst and more
detailed comment on the economic parameters the investigations should be contineued.

Conclusions
This article optimized operating parameters of contineous catalytic naphtha reforming of
Bandar Abbas Refinery with using the lumped kinetic model with twenty-six lumps.
 7th International Chemical Engineering Congress & Exhibition
Kish, Iran, 21-24 November, 2011

Optimization of the operating parameters including temperature, pressure and hydrogen to

hydrocarbon ratio was conducted for a unit with three or four beds by the mathematical model
to construct the table of response surface method for RON and the liquid yield by conducting
30 times running the mathematical model in the studied ranges of operational conditions. It
was concluded that using three reactors instead of four, required around 17k increase in the
inlet temperature of the reactors to approach to the same industrial target of RON and yield of
reformate.
The present simulator could be an appropriate tool for prediction of the optimal conditions
before performing any changes in industrial scale for prediction of the outlet yield and RON
of reformate with 95% certainty.

References
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 Optimization of Operating Parameters of Continuous Catalytic Naphtha ……

Nomenclature
P partial pressure ∆H heat of reaction
F flow rate Cp heat capacity
T Temperature n carbon number
C coke content ρ Density
r rate of reaction R bed radius
r0 rate of reaction when catalyst is fresh L reactor height
φ deactivation function α deactivation constant

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