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International Journal of Chemical Engineering and Applications, Vol. 1, No. 2, August 2010
ISSN: 2010-0221
I. INTRODUCTION
Catalytic naphtha reforming is an important process for
producing high octane gasoline, aromatic feedstock and
hydrogen in petroleum-refining and petrochemical
industries.
Advanced process control and process optimization
strategies are important to be considered in catalytic
reforming of naphtha due to its impacts on refineries profit.
These are achieved mostly via a reliable mathematical
dynamic model.
The catalytic reforming process came into operation in
refineries in the late 1940s. The reforming of naphtha feed
stocks over platinum catalysts was pioneered by Universal
Oil Products (UOP), with the plat forming process introduced
in 1947.
Concerning the kinetic modeling of the naphtha processes
Smith [1] firstly proposed a four lumps model by considering
naphtha as being composed of naphthenes, paraffins,
aromatics and light hydrocarbons (<C5), lumps with average
carbon number properties in 1959. However, it is not much
precise because of its limited lumps. Kmak [2] developed a
detailed model (Exxon model) including twenty-two lumps,
which was refined by Froment [3] who developed a more
detailed twenty-eight lumps model with 81 reactions.
Ramage [4] developed the Mobile thirteen lumps model that
considered the adsorption of chemical lumps on the catalyst
surface.
More recently Jorge [5] presented a twenty-four lumps
model with 71 reactions and Taskar [6] proposed a more
detailed thirty-five lumps model used for the optimization of
semi-regenerative naphtha catalytic reformers. Generally
speaking, detailed models are theoretically sound but quite
complicated, consequently difficult for application because
of very complex lumping scheme and parameter estimation to
maintain a good balance between kinetics, simplicity and
applicability of the model [7].
On the other hand, dynamic modeling was performed by
Yongyou et al. [15] by a 17 lumps kinetic model and solution
was performed after linearization. Actually, very limited
attempt on dynamic simulation of this process have been
appeared in the literature. A modeling and dynamic
simulation on the catalytic reforming process was carried out
by Ansari [16] using Smith's kinetic scheme.
A. Process Description
Catalytic naphtha reforming contains three reactors in
series, as shown in Fig. 1. It is generally carried out in
three/four fixed or moving bed reformers. The catalyst used
in reformer is commonly a bifunctional bimetallic catalyst
such as Pt-Re/Al2O3, providing the metal function and the
acid function. The product stream from the first reactor after
preheating enters the second reactor and similarly the product
stream from the second reactor after preheating enters the
third one. Thus, the reactor feeds are raised to the proper
temperature by heaters located before the reactors, since the
reactions are endothermic. The product stream from the final
reactor enters a separator wherein hydrogen rich gas stream is
separated from the products which is then recycled back and
mixed with the first reactor fresh feed. Reactors are of
different sizes, with the smallest one located in the first stage
and the largest one in the last. Temperature profile of the
reactors is shown in Fig. 2.
1,2
Research Institute of Petroleum Industry (RIPI), West Blvd. Azadi
Sport Complex, Tehran, Iran
3
Assistant Professor, School of Chem. Eng., Iran Univ. Sci. Tehran., Iran
Corresponding author: Tel.:+982148252503; fax: +982144739713
E-mail address: Shokris@ripi.ir
159
International Journal of Chemical Engineering and Applications, Vol. 1, No. 2, August 2010
ISSN: 2010-0221
dFi nr
d ( ci )
+ i , j rj =
dw j =1
b dt
(1)
Where:
yi =
ci
c
i =1
Ft =
nc
Fi
nc
F
i =1
m
M av
(2)
(3)
nc
M av = yi M i
(4)
Fi = yi Ft
(5)
i =1
( C pcata +
ci C pi )
i =1
H i = H 0 + C pi dT
(7)
T0
160
International Journal of Chemical Engineering and Applications, Vol. 1, No. 2, August 2010
ISSN: 2010-0221
C. Furnace Model:
Simple model of fired heater furnaces are used here.
In the mathematical model of this system the following
assumptions are used:
1) Outlet gas temperature from the furnace is equal to tube
wall temperature
2) The temperature of the tube wall is equivalent over the
length of tube
3) Variation of gas temperature inside tube is linear
We consider the tubes for heat transfer according to fig.3
(12)
dt
= Fcold ( H cold ,i H cold , o ) q
d (C p , hot M hotThot , o )
(13)
dt
= Fhot ( H hot ,i H hot , o ) q
The heat transferred q is:
(14)
q = F U A Tm
Tm =
ln(
E. Octane Number:
Octane number of the product from naphtha reforming unit
can be expressed by concentrations as follows [14]:
n
(16)
RON = b W
(8)
dt
.
= q (T f , out T f , in )C p f m f
Where,
T f ,m =
(T f , in + T f , out )
r =1
dt
q (T f ,out T f ,in )C p f m f
(mwC p w +
m f C p f d (T f ,in )
mf Cp f
2
dt
(9)
Thot ,i Tcold ,o
)
Thot ,o Tcold ,i
(10)
161
International Journal of Chemical Engineering and Applications, Vol. 1, No. 2, August 2010
ISSN: 2010-0221
714.5
714
713.5
713
2000
4000
6000
8000
10000
12000
time (sec)
(17)
Output temp. of second reactor
y = cx 2 + bx + a
Slope is calculated from the equation:
dy
= 2cx + b
dx
(18)
744.6
744.5
744.4
744.3
744.2
744.1
744
743.9
2000
4000
6000
8000
10000
12000
time (sec)
763.7
763.6
763.5
763.4
763.3
763.2
763.1
763
2000
4000
6000
8000
10000
12000
time (sec)
V. CONCLUSION
In this paper, simulation of the dynamic model of the
catalytic naphtha reformer process by MATLAB software is
presented. The kinetic parameters of model are based on the
steady state condition and are obtained from a commercial
plant data furnished by a domestic petroleum refinery. This
dynamic model is in form of partial deferential equations.
The nonlinear model of the system was solved numerically
by MATLAB software.
The simulation results reveals of satisfactory fitness
between data and the model.
162
International Journal of Chemical Engineering and Applications, Vol. 1, No. 2, August 2010
ISSN: 2010-0221
NOMENCLATURE
Ac
ci (kmol / m3 )
nc
d ( Fi H i )
nc
dw = ( Fi
i =1
dw
i =1
d p( m )
Catalyst diameter
E Aj
Activation energy
G( kg / m 2 .s )
nc
( H i
i =1
dEsys
Reaction Rate
dt
nc
dEcata
dH i
dw + ni
dt
dt
i =1
nc
+ Hi (
i =1
APPENDIX A
Mass balance equation for element of catalyst weight in a
plug flow reactor is:
nr
j =1
(19)
d (ni ) d (ci )
=
dw
dt
dt b
dE sys
dt
nc
ni = ci
dw
b
(20)
d (ci )
dFi nr
+ i , j rj =
dw j =1
b dt
H
i =1
dE cata
dw +
dt
nc
( Fi C pi
(21)
i =1
FH
i =1
Fi H i
i =1
=
w + dw
dt
dFi
+
dw
nr
j =1
nc
n
i =1
dH i
+
dt
r ) dw
i, j j
(27)
d (P)
dw
dt b
dT
dT
) = C pcata
+
dw
dt b
nr
nc
j =1
i =1
nc
c C
i =1
pi
dT
dt
(28)
+ r j ( H i i , j )
dEsys
(26)
APPENDIX B
nc
dw
b
nc
dw dci d ( PV )
)
b dt
dt
V =
Fi.w Fi , w + dw + i , j rj dw
(25)
dn d ( PV )
+ Hi i
dt
dt
i =1
i =1
nc
Fluid Density
( m2 )
d ( Ecata + ni ( H i PVi ))
dt
nc
dEcata
dH i
=
dw + ni
dt
dt
i =1
Gas constant
f ( kg / m )
dFi
)dw
dw
nc
Viscosity
(24)
( pa.s )
ri (kmol / kg cat.s)
R
s ( kg / m 3 )
dH i
)dw
dw
dT
=
dt
(22)
( Fi C pi )
i =1
nc
dT nr
rj ( H i i , j )
dw j =1 i =1
( C pcata +
b
nc
c C
i =1
pi
(29)
d ( Fi H i )
i =1
dw
REFERENCES
dw =
dEsys
dt
[1]
(23)
[2]
[3]
163
International Journal of Chemical Engineering and Applications, Vol. 1, No. 2, August 2010
ISSN: 2010-0221
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
164