Modelling and Simulation of Commercial Catalytic Naphtha

Reformers
GARIMELLA PADMA VATHI and KUMAR K. CHAUDHUW
Research Centre, Indian Petrochemicals Corporation Limited, Baroda - 391 346, India
A simulation model for catalytic reforming has been developed to monitor commercial plant performance. The model
consists of various modules to predict temperature and concentration profiles, catalyst deactivation and cycle length,
inter stage heater duties, recycle gas composition and octane number. The lumping details of the feed and reaction
scheme, parameter estimation and model validation details are given. The model numerically integrates the component
and energy balance equations for the combined feed and recycle gas in each reactor and then simulates flash separator
for recycle gas composition. The results of the model validated for four different commercial reactors performance are
presented.
On a mis au point un modele de simulation pour le reformage catalytique afin de contrbler la performance d’une instal-
lation commerciale. Le modele comporte divers modules pour predire les profils de temperature et de concentration, la
desactivation du catalyseur et la duree du cycle, les charges thermiques des systemes de chauffage entre les etages, la
composition du gaz de recyclage et le nornbre d’octane. On donne des details globaux sur le schema d’alimentation et
de reaction, I’estimation des parametres et la validation du modele. Le modble integre numeriquement les equations des
bilans d’energie et des composants pour I’alimentation et le gaz de recyclage combines dans chaque reacteur, puis il
simule le separateur flash pour la composition du gaz de recyclage. On presente les resultats du modele valides pour quatre
performances de reacteurs commerciaux differents.
Keywords: naphtha reformer, lumped kinetics, catalyst deactivation, modelling, simulation.

from paraffins. Jenkins and Stephens (1980) considered sev-

C atalytic reforming of naphtha is one of the best methods
for producing high octane gasoline and aromatics in
petroleum refineries and petrochemical industries. A cat-
alytic reformer model which can monitor day to day perfor-
mance of plant in terms of yield, temperature drops across
the reactors, heaters duty, cycle length and optimize the
process for maximum profit and simulate during design of a
new reformer or revamping the old units is of particular
interest to all the people in the business. In todays competi-
tive market this type of model is absolutely necessary for
any industry for making decisions regarding catalyst and
process selection and performance.
The naphtha feed is very complex consisting of several
hundred components and each of them undergoes various
reactions. A detailed model considering all the components
and reactions is very complex and hence a proper lumping
of the components by carbon number based on similar prop-
erties and kinetic behavior would be more convenient.
Smith (1959) developed a model considering naphtha as
naphthenes, paraffins, and aromatics lumps with average
carbon number properties. However the early models were
limited to start of cycle kinetics (Smith, 1959; Krane et al.,
1959; Zhorov et al., 1965, 1970; Wolff and Kramarz, 1979).
The deactivation of the acidic function of the catalyst was
included in the model by Henningsen and Nielson (1970).
They reported the frequency factors and activation energy
values of different reforming reactions of Cs naphtha. Their
results indicated a linear relation between catalyst activity
and reactor inlet temperature. Kmak and Stuckey (1973)
studied reforming over a wide range of operating conditions
using pure components, mixtures and naphtha feed and
developed a detailed model. Zhorov et al. (1980) considered
C,, C, lumps of naphtha and direct formation of aromatics
*Author to whom correspondence should be addressed. E-mail address:
ipcl@giasbmol.vsnl.net.in
IPCL Communication NO. 320
enty-eight reactions involving thirty one components and
calculated pressure exponents. Ramage et al. (1980, 1987)
published a detailed complete model considering C,-C,
lumps of naphthenes, paraffins and aromatics. They have
included internal diffusional effects also. The model pub-
lished by Bommannan et al. (1989) is a simple kinetic model
similar to that of Smith’s (1959), including catalyst deacti-
vation. Turpin (1995) discussed the typical refinery prob-
lems that can be solved accurately using process simulation
model. In the present model the naphtha feed and reforming
products are considered in twenty-six hydrocarbon lumps
which undergo major reforming reactions such as dehydro-
genation, dehydrocyclization, isomerization, hydrocracking
of naphthenes and paraffins, and hydrodealkylation. The
catalyst deactivation due to coking has been considered by a
function decreasing exponentially with coke content on cat-
alyst. The kinetic parameters of the reforming reactions are
obtained from commercial plant data of first few days by
minimizing the difference between the predicted and the
actual plant values.
Main reaction model
FEED
The feed to the reforming unit is straight run naphtha dis-
tilled to obtain a narrower cut of required boiling point to be
reformed. The boiling point of the feed varies depending on
the type of process and products needed like gasoline or
aromatics. In the present model for reforming, the naphtha
feed has been characterized by naphthenes (alkyl cyclo-
hexanes (ACH) and alkyl cyclopentanes (ACP)), paraffins
(normal paraffins (A!.), and is0 paraffins (IP)),and aromat-
ics (A) lumps of each carbon number from C&. The feed
combined with recycle gas that contains C, to C, gases and
hydrogen amounts to total twenty-six lumps. The splitting of
paraffins (NP, IP)and naphthenes (ACH, ACP) is optional

930 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 75, OCTOBER, 1997
 depending on the availability of feed composition of indi- DEHYDROCYCLIZATION
vidual species.
ACHn + H2 f) NP,;% = ~ ~ , ( P A C H , ,--)
PH ~
pNPn = r3,
CATALYST
d6 K3n
In reforming a bifunctional catalyst is used in which an .......................................... (3)
acidic function provided by a chlorided alumina carrier is
combined with a metal function provided by platinum or
platinum with a second metal such as Re, Ge, Ir, etc. High
metallic surface is required for dehydrogenation reaction
where as acidic function promotes all other reforming reac- .......................................... (4)
tions such as dehydrocyclization, isomerization, hydro-
cracking reactions. NP, t) ACP, +H 2 ; 5 = k5,(PNPn- pACHnpH2 = ,.5,
REACTIONS d6 K5 n
.......................................... (5)
The twenty-six lumps of hydrocarbons discussed above
are connected by major reforming reactions considered in
this model. IP, e ACP, + H 2 ; s = k6,(Plpn - = r6,
The dehydrogenation of cycloparaffm is catalyzed by the d6 K5 n
metal function of the catalyst and is the fastest of all the .......................................... (6)
reforming reactions. This reaction increases the octane num-
ber of the product. It is an endothermicreaction. An increase ISOMERIZATION
in molar mass of cycloparaffms favours the thermodynamic
feasibilityof the formation of aromatics. It is favored at high
temperature and low pressure. (7)
The isomerization of alkylcyclopentanes to alkylcyclo-
hexanes is followed by dehydrogenation to aromatics. The
isomerization of normal paraffins to isoparaffms is highly PARAFFINS CRACKING
desirable reaction as the naphtha feed consists more per- 5
centage of normal paraffins which are isomerized to n n pNPn
isoparaffins having high octane number. These are moder- N P n +3- H 2 ’ - C 15
C i ;i=l k g n ( - ) = r 84
d X 8 n =d6 ,. . (8)
ately fast reactions catalyzed by acid sites and the reaction
rate increases with increasing temperature and pressure.
The dehydrocyclization of paraffins to naphthenes is a 5
comparatively slow reaction. The rate is comparable to that IP, +-H2
n + - Zn C i ; - =k9,(%)=r9, . . . (9)
of hydrocracking. The thermodynamic feasibility of the 3 15 2.= 1 dtl &
reaction increases with increasing carbon number. The reac-
tion is favoured at high temperature and low pressure. NAPHTHENES
CRACKING
Hydrocracking is exothermic reaction and the reaction rate
increases with increasing temperature, pressure and paraffin 5
carbon number. Hydrocracking of naphthenes is less than that ACH, +-H2
n-3 + - xn C i ; - - aYlon - kIon(h)=r10,
of paraffins. In naphthenes, cyclopentanes are more suscep- 3 15 i= I d6 4
tible to cracking than cyclohexanes. The cracking of naph- ..........................................
thenes and paraffins and the hydrodeakylation reactions are (10)
irreversible. All other reactions are reversible reactions.
5
Hydrodealkylation is the slowest of all the reforming
ACP, +-H2
n-3 + - znC i ; - =klIn(h)=rll,
reactions. The rate increases with increasing carbon number.
It is an exothermic reaction and is favoured at high temper- 3 15 i=l 4 d6
atures and pressures. The reaction network proposed in this .......................................... (1 1)
model and corresponding rate equations are presented below. n = 6-9 for all the reactions from Equations (1) to (1 1).
DEHYDROGENATION HYDRODEALKYLATION

.......................................... (1)
..........................................
k = A exp(-EIRT) The material balance equations are given below

RING EXPANSION = -r2, + r5, + r6, - r l 1, ............ (13)

d6

&ACH~ = -rl,
d6
+ r2, - r3, - r4, - r10, . . . . . . . . (14)

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 75, OCTOBER, 1997 93I

-
dx,, -
dt3
- r3, - r5, - r7, - r8, . composition the subroutine FLASH is used. The FLASH
-= r4, - r6, + r7, - r9, . . . . . . . . . . . . . . .
do
-
&A6 = ri6 + ~ 2 ~& ;~ -7 = r17 - r126 + r 1 2 ~
do do
-=rig
&A8 -r127 +rl2g;- dxA9 =r19-r128
dt3 dt3
dx n reduces the yield and selectivity with time on stream. This
2= 3r1, - r3, - r4,
dt3
+ r5, + r6, - -(r8,
3
--( n - 3 ) ( r 1 ~ , + r l I,) -r12, . . . . . . . . . . . . . .. . (18)
3 temperature as after a certain value it can not yield reformate
HEATBALANCE
9 12
dT m . . . . . . . . . . . . . . (19)
-
do = CCC
n=6 i=l
)rin )=
PROCESS
The major reforming reactions are endothermic produc-
ing a decrease in temperature of the reaction stream and cat-
alyst along the bed which decreases the reaction rate. To
avoid this, the total catalyst is distributed in three or four
adiabatic reactors with interstage heaters before each reac-
tor. The naphtha feed is mixed with recycle gas and heated
to the desired temperature before entering the first reactor.
The reaction temperature in the first reactor decreases rapidly
due to the dehydrogenation of naphthenes to aromatics. The
outlet of the first reactor is reheated and fed to the second
reactor where mostly the isomerization takes place. From
the second reactor the effluent is again reheated before
entering the third reactor. The temperature drop across the
third reactor is very less which is due to the exothermic
cracking reaction. Dehydrocyclization and cracking takes
place in the third reactor.
The first reactor is always smaller than the other reactors
and the last reactor is always the largest. The catalyst load-
ing in the first reactor is in the range of 8-20% of total cat-
alyst. The outlet from the third reactor section is cooled and
separated in to gaseous and liquid products in a flash sepa-
rator. The gaseous products consists of C,-C4 paraffins with
60-90 mol% of hydrogen. This gas is recycled to the inlet of
first reactor where it is mixed with naphtha feed with hydro-
gen to hydrocarbon mole ratio in the range between 5 and
10. The liquid product is called reformate which mainly
consists of aromatics (60-70 mass% of naphtha feed) and
saturates in the C -C9 carbon number range.
The model incfudes modules to simulate feed and inter-
stage heaters, flash separator, and to calculate octane number.
The simulation of feed and interstage heaters are to calculate
heat duty and to check capacity limitations. It is obvious for
any specified operating conditions violation of capacity limit
indicates that such operating conditions are not feasible and
the predicted results have no practical use. The heat duty is
calculated using simple heat balance equations.
The recycle gas composition is one of the important
inputs to the model as its composition varies with the reactor
932 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 75, OCTOBER, 1997
performance. Hence, for the accurate prediction of recycle
subroutine includes isothermal equilibrium flash calculation
at a given separator temperature and pressure. The flash cal-
(16) culation needs precise prediction of equilibrium constant.
Hilderbrand’s correlation has been used to calculate liquid
phase activity coefficient (Chaoand Seader, 1961) and stan-
dard thermodynamic relations have been used to calculate
equilibrium constants.
Deactivation model
. . . . (17)
In catalytic reforming of naphtha the catalyst gets deacti-
vated by coke deposition which blocks the active sites and
+ r9,) deactivation effect is compensated by increasing the operat-
ing temperature so that the yields of primary products are
kept constant. However, there is a limit to increasing the
of desired quality. Then the catalyst has to be regenerated to
be used in the next cycle of operation. To predict the behav-
ior of such reactions subject to catalyst deactivation, the
mathematical model should also include the coking rate
equation. Many articles have been published on modelling
of catalyst deactivation due to coking, beginning with
Voorhies (1945) who correlated coke deposition to time on
stream. Froment and Bischoff (1961, 1979) related catalyst
activity to the amount of coke deposited on the catalyst sur-
face. It has been reported (De Pauw and Froment, 1975;
Marin and Froment, 1982; Van Trimpont et al., 1988) that
both the reforming and coke reactions decrease exponential-
ly with coke deposited on the catalyst. Wolf and Peterson
(1977) used more fundamental approaches based on kinetic
expressions to model coking. In a recent paper by Beltramini
et al. (1991), the deactivation of both the acid and metal
function activities of the catalyst has been taken into con-
sideration. In the present investigation, the deactivation is
taken in to account by a fhction decreasing exponentially
with coke content on catalyst. The rate equations ate reformu-
lated accordingly by introducing a deactivation function, 0,
ri,(t) = ri,(O) 0 , O S 0 S 1. . . . . . . . . . . . . . . . . . . . (20)
where ri,(O) is reaction rate at start of cycle conditions when
coke content is zero, and ri,(t) is rate of reaction at time t.
The ratio of reaction rate at time t to start of cycle rate gives
the deactivation function value. The rate equation corre-
sponds to start of run conditions when 0 is 1. The deactiva-
tion function can be expressed in terms of coke deposition
which is the real cause of deactivation.
The coking rate equation is
(21)
Both the reforming reaction and coking rate decreases
exponentially with coke content on catalyst. A common
deactivation function 0 expressed as
0 = exp(-aC). ............................ (22)
is used. By substituting Equation (22) into the coking rate
Equation (2 1) and integrating for coke yields
1
C = (-)ln(l + a mot)....................... (23)
a
 TABLE 1(~) TABLEI(B)
Heat of Reaction, EIR and InA Values Equilibrium Constants
Heat of reaction (kJ/mol of H2 consumed or produced) Keqi = exp(AI-B1iT) kPa3 A' B'
In A
AH (EIR) x 1r3 kmolhkg ACHt)A 6' 60.4706 25240.9
kJ/mol K cat.kPa C, 60.5908 25430.2
C8 60.1909 23973.9
Dehydrogenation c
6 -73.52 19-50 18.88 60.7522 23911.6
c
9
C7 -71.89 19.50 19.36
C, -67.24 19.50 19.53 Keqi = exp(A'-B1/7) kPad
C, -65.23 19.50 20.38
Dehydrocyclization C6 45.47 33.1 1 24.37 ACHo NP 6' -9.3604 -5250.233
ACH f) NP** C, 37.26 33.1 1 24.43 c7 -1 0.4890 4085. I48
C, 30.56 33.1 1 27.61 c, -10.5665 4 6 1 7.1 93
c, 41.45 33.1 1 29.76 c
9 -I 0.4140 -4476.830
ACH c)IP** C, 52.17 33.1 1 26.36 ACH t)IP '6 -1 1.3262 -6526.178
C, 43.63 33.1 1 26.76 -12.971 0 -5207.850
C, 47.86 33.1 1 28.96 C,
c, 47.39 33.1 1 29.76 c, -1 3.5994 -5499.379
c
9 -1 1.21 1 1 -5284.957
ACP + NP** C, 60.16 33.11 24.04
C, 60.38 33.1 1 24.24
C, 60.17 33.1 1 25.23 TABLE 2
C, 60.37 33.1 1 27.20 Material Balance
ACP + IP+* c
6 66.87 33.1 1 24.37 flow rate kgh
C, 66.74 33.11 24.43 Input
C, 66.1 1 33.1 1 27.61 Feed 14,999
C, 66.36 33.1 1 29.76 output
NP + ACP c, 40.19 33.1 1 29.07 C5+ reformate
Off gas
12,734
400
C, -60.38 33.1 1 29.13
C, -60.17 33.1 1 31.31 Purge gas 1,886
C, -60.38 33.1 1 32.96 Total 15,020
Material balance error 0.14%
IP + ACP C, -66.89 33.11 29.07 (mass of feed - mass of products) x 1 OO/mass of feed
C, -66.74 33.1 1 29.13
C, -66.1 1 33.1 1 31.38
C, -66.36 33.1 1 32.96 Intermediatecoke contents can be estimated using the fol-
Cracking of lowing relation with coke content measured at the end of the
ACH and ACP* C, 50.91 34.61 42.0 run
C, 47.82 34.61 42.5
C, 50.07 34.61 43.5
C9 50.58 34.61 44.0
NP C, 56.36 34.6 1 40.3
C, 55.69 34.6 1 40.5
C, 55.23 34.61 40.6 where exp(aC($))could be calculated from end of run deac-
C, 55.14 34.61 42.5 tivation function. No distinction was made between coke
Cracking of IP C, 49.66 34.61 40.5 deposited on the acid function and coke deposited on metal
C, 50.91 34.61 40.6 function.
C, 51.67 34.61 40.7
C, 52.17 34.61 42.5 Parameter estimation and model validation
Hydrodealkylation' C,-C, 47.585 17.92 5.57
The heat of formation, free energy of formation and spe-
Isomerization C, 6.699 26.00 24.48 cific heats at different temperatures are taken from MI data
NP+ IP C, 6.364 26.0 24.48
c, 5.945 26.0 24.88 book (1975). The equilibrium constants are calculated from
c, 5.945 26.0 24.88 thermodynamic relation AGO = -RTlnK. The rate constants
follow an Arhenius relation, k = A exp(-EIRT). The kinetic
IP + NP C&-6.7, -6.3, -5.9, -5.9 26.0 22.20 parameters, A and E, are taken from the literature (Smith,
ACH + ACP -14.6.-23.0.-18.4.-18.8 26.0 26.08 1959) and from pilot plant performance data as an initial
ACP+ ACH 14.6,23.0, 18.4, 1818 23.81
basis and then these are fine tuned to the commercial plant
Units of A: ** kmoyh.kg cat.kPa2; data. The operating and performance data of fust few days
* kmol/h.kg cat.; of the commercial reformer are used to estimate the kinetic
+ kmol/h.kg ~at.kPa'.~. parameters by fine tuning. The fine tuning is done by mini-
mization of the sum of the squares of the deviations between
the plant and the calculated values of aromatics conversion
a and rco can be estimated fiom experimental coke vs time data and temperature drops across each reactor for a given set of
using an optimization subroutine such that C(Ciev.-Cw,.ed.)2 operating conditions corresponding to start of cycle. The val-
is a minimum. ues of heat of reaction, activation energy and pre-exponential

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 75, OCTOBER, 1997 933
 TABLE 3
Operating Conditions
Case 1 Case 2 Case 3 Case 4
Number of reactors 3 4 3 3
Total
Catalyst (kg) 6818 17,500 18,415 6,090
Catalyst loading (mass%)
8.5 17.10 20.0 19.2
Rl
12.6 27.30 40.0 40.4
zn MI-
R2
R3
78.8 27.80 40.0 40.4 z -
I-
27.00 40-
R4
Feed P c6 0.17 0.07 37.0 11.51
(mass%)
27.47
620 -
C, 5.36 6.35 8.0 I , I , I , I , I

4 co
27.05
7.96
27.71
4.51
25.87
1.91 o
?' CATALYST DISTRIBUTION
N Ci 1.05 0.95 28.0 5.58
12.33 12.77 4.0 14.00 Figure I(a) -Temperature profiles (case I).
Cl
'8 22.94 22.49 6.60
c9 4.91 10.70 0.47
A '6 0.15 0.17 22.9 0.00 1 I 1
Cl 4.88 5.22 0.1 0.49
8' 12.82 9.06 4.08
c9 0.38 0.00 2.02
Feed flow rate 11,960 41,300 28,750 10,170
(kg/h)
H2/HC mole ratio 5.5 6.0 4.8 5.5
Inlet temperature to reactors ("C)
TI 496 491 51 1.4 485
l2 501 494 511.2 485
l3 508 497 511.7 485
T4 497
Pressure (kPa) 1824 1774 2889 2736

Table 4
Comparison Between Predicted and Reported Values
Figure I(b) -Concentration profiles (case I).
Case 1 Case 2 Case 3 Case 4
Actual Pred. Actual Pred. Actual Pred. Actual Pred.
ATI(K) 84.0 84.80 89.0 90.40 42.2 42.60 60.0 58.3
A n ( @ 33.0 32.00 35.0 35.95 5.0 2.70 21.0 21.2
22.0 21.80 18.0 16.33 4 . 8 -3.60 4.0 4.1
'""1
AT(K) 139.0 138.60 142.0 144.13 42.4 41.70 85.0 83.6
Yields (%mass/mass)
H2 2.70 2.72 2.5 2.58 0.87 1.37
c, 2.40 2.47
2.60 2.56
1.5
2.0
1.32
2.48
1.96
3.77
2.25
4.22
c2 4.30 3.91 3.9 3.68 5.80 6.19
c3
3.30 4.50 4.8 4.91 7.67 8.15
-
c4

2
'SA 1.2 1.16 1.1 1.06 41.7 41.52 MOOEL PR E DlCTlO NS
C.# 16.0 16.18 18.6 18.08 3.6 3.96
C& 40.2 40.40 34.2 34.41 - -
C4 6.0 5.10 11.2 11.34 - - 0
TA 63.40 62.80 65.1 64.89 45.3 45.56 TIME ON STREAM I h l
LY 83.7 83.77 85.0 85.00 80.0 79.93 77.81 77.82
Figure 2 - Comparison between predicted and plant yields as a
GY 16.3 16.23 15.0 15.00 20.0 20.07 22.19 22.18
function of time on stream: (case I).

factor to calculate rate constants of various reforming reac-
tions used in this model are presented in Table l(a). Table
l(b) gives constants used to calculate equilibrium constants
of reversible reactions. The input to the model are feed flow
rate and composition of all the lumps mentioned above in
the feed, catalyst loading, recycle gas composition, inlet
reactor temperatures and pressures. The model integrates
numerically the component and energy balance differential
equations for the combined feed and recycle gas by fourth
order Runge-Kutta method for each individual reactor and
then goes to the simulation of the flash separator to calculate
recycle gas composition which involves successive substi-
tution. The next step is estimation of the deactivation func-
tion using the SOR kinetic parameters for the complete cycle
to maintain desired conversion throughout the cycle with
increasing temperature. The output of the model includes
temperature and concentration profiles of reformate as a
function of catalyst distribution for each reactor, gas com-

934 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 75, OCTOBER, 1997
 TABLE5
Effect of Feed Throughput, H21HC, and Catalyst Loading on Yield
TI = 496; 12 = 501; 73 = 508°C
Feed Base 1O%> 1O%<
kgh 11,860 Base Base
H2lHC 5.5 5.5 5.5 4.5 6.5 5.5 5.5 5.5 5.5
Catalyst (kg)
R1 579 579 579 579 579 479 679 579 579
R2 863.5 863.5 863.5 863.5 863.5 863.5 863.5 763.5 963.5
R3 5375.00 5375.00 5375.00 5375.00 5375.00 5475.00 5275.00 5475.00 5275.00
Yields (%mass/mass)
1.93 1.88 2.01 1.97 I .92 1.95 1.94 1.95 1.95
A1 15.69 15.48 16.01 15.87 15.6 1 15.76 15.71 15.70 15.70
40.20 40.28 40.09 39.92 40.42 40.12 40.26 40.18 40.22
8.15 8.2 1 8.08
2 83.75 84.48 82.69
8.06
83.58
8.2 1
83.69
8.13
83.53
8.15
83.70
8.14
83.61
8.14
83.61
Heater-1 Duty MMkJh
5.82 6.406 5.27 5.61 6.03 5.74 5.86 5.82 5.82
Heater-2 Duty
2.55 2.805 2.30 2.64 2.51 2.64 2.55 2.55 2.59
Relative cycle length
1.oo 0.824 1.10

LY

. 60 TA

-r I
20 - - '
4 A
II
.R3RL -
0
-
C9A
\ c6A
I 1 I
2000 w 6000 8000 10wo
TIME ON STREAM I h l

Figure 4 -Variation of yields with time on stream (case 2).

positions, temperature drop and heat duty of the interheater
at the exit of each reactor. The output also includes the
octane number of the reformate and catalyst cycle length.
The octane subroutine which calculates the octane number
of the reformate consists of octane number data base of sev-
eral pure components of naphtha feed and reformate.
Results
Before using the plant data for model validation and simu-
lation, the reliability of data has been tested by checking the
material balance. The sample case material balance is pre-
sented in Table 2. The model has been validated for four dif-
ferent commercial reformers with different product profiles,
feed stock compositions, number of reactors and operating
conditions. The operating conditions and SOR results of these
four cases are summarized in Tables 3 and 4, respectively.
CASE1
The model is validated for a commercial reformer consist-
ing of three reactors for xylenes production. The concentration
and temperature profiles of this reforming process as a func-
tion of catalyst distribution are shown in Figures l(a) and
I@), respectively. The comparison between actual and
model predicted values of total liquid and Cs aromatics
yields as a function of time on stream is shown in Figure 2.
The plant performance data is collected for one complete
cycle to obtain a relation between time on stream, tempera-
ture and deactivation fbnction and keeping that as basis the
cycle length of next cycle is predicted which is found to
agree with the plant reported value.
A kinetic model is useful to solve typical problems in the
plant operation and can be used to study the effect of vari-
ous independent operating parameters on dependent vari-
ables. Here the model is applied to study the effect of feed
throughput on catalyst relative cycle length, effect of
hydrogen to hydrocarbon ratio and catalyst loading on per-
formance; the results are presented in Table 5. It is
observed that an increase in feed throughput needs an
increase in weight average inlet temperature (WAIT),
which is defined as the sum of the product of the inlet tem-
perature to each reactor multiplied by the weight percent-

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 75, OCTOBER, 1997 935

3.0
-c MOOEL PREOICTIONS
241
2'2
2.0
t I
ZMM
I
MOO 6000 Boo0
TIME ON STREAM IhJ
Figure 5 - Variation of hydrogen yield with time on stream
(case 2).
age of the total catalyst in that reactor to maintain same
product quality. For 10% increase in feed, the increase in
WAIT is between 2 and 2.5'C to maintain the same octane
number. The improvement in the yield with a 10% increase
in feed throughput is insignificant compared to the corre-
sponding increase in heat duty. Similarly, with reduction in
feed throughput the WAIT reduces. The relative cycle
length increases with decreasing feed rate as shown in
Table 5. An increase in hydrogen to hydrocarbon ratio
increases the cycle length. The significant difference
observed in the temperature drops across the reactors with
varying H,/HC value indicates that the temperature drops
across the reactors depend on the reactions occurring and
the H,/HC value. The effect of catalyst distribution is stud-
ied by increasing the catalyst load by 1.5% in one reactor
and keeping the load of one of the other two reactors and
the total catalyst load constant. The increase in catalyst load
in the first and second reactors improves aromatics yield.
So, when needed and when the catalyst of a reactor is not
fully utilized, the catalyst load can be redistributed to
improve the yields.
CASE2
Here also the model is validated for a commercial system
producing xylenes but consisting of four reactors in series.
The deactivation function is estimated for complete twelve
months cycle as a function of first reactor inlet temperature
to maintain constant desired aromatics yield. The variation
of catalyst activity as a function of time on stream is
obtained from Equation (24). The variation of temperature
drop across each reactor against time on stream for the com-
plete cycle is shown in Figure 3. Figures 4 and 5 give the
predicted values of aromatics yields of each carbon number
from C&, total aromatics yield, total liquid yield and
hydrogen yield, respectively, as a function of time on
stream. The desired aromatic products (toluene and xylenes)
are maintained constant from SOR to EOR.The hydrogen
yield decreases from SOR to EOR. The model predicted val-
ues are compared with available reported values at SOR and
EOR conditions which matched very well (Figures 4 and 5).
The first reactor inlet temperature and deactivation function
could be correlated as given below.
0=20.5-0.04T(Tin°C) . . . . . . . . . . , . . . . . . . (25)
936 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 75, OCTOBER, 1997
MODEL PREDICTIONS Ly
- 80-0
0
J
P
'c
I
10 0
0
o[ ;G
-
I
48
:6*
12
TIME ON STREAM l h l
Figure 6 - Comparison between predicted and plant yields as a
hnction of time on stream (case 3).
CASE3
The model is validated for commercial reformer operat-
ing for production of benzene and toluene. In this case, the
naphtha feed consists of only C, and C7 lumps of naph-
thenes, paraffins and aromatics species. Figure 6 gives the
predicted and the plant aromatics yield and the total liquid
yield against time on stream.
CASE4
In this case, the process objective is to obtain a reformate
of research octane number of 90 for feed research octane
number of around 52. The predicted and actual yields and
temperature drops across the reactors are presented in Table 4.
Overall, for all the cases the obtained agreement is satis-
factory in view of the scatter observed generally in com-
mercial plant data. Though it is not shown here, the model
results for various cycles and cases were equally close to
plant performance, thus allowing us to conclude that the
reaction scheme and kinetic parameters are adequate enough
to predict individual yields of all the important desired prod-
ucts. It is observed that the predicted heat duty values in all
the four cases are agreeable with the reported values.
Conclusion
A model has been developed for simulation of catalytic
reformer. The kinetics were derived from pilot and com-
mercial plant data. The heaters and flash separator are also
modelled. Kinetics for various commercial catalysts can be
derived and built in to the model so that for a specific plant,
performances of various catalysts can be predicted without
changing the catalyst. The model along with deactivation
h c t i o n predicts the reformer performance in terms of reac-
tor temperature drops, temperature and concentration profiles
of each reactor, individual yields of reformate, hydrogen and
C,-C,, total liquid yield, duty of heaters at the end of each
reactor, and reformate octane number at any time on stream.
By applying the model it is possible to select optimum oper-
ating conditions for complete cycle, number of reactors,
interstage heaters, and catalyst loading required for com-
mercial operation. The comparison of model values with
actual values for four different commercial reactor systems
covering wide ranges of operating conditions and product
profiles is presented.
Nomenclature Henningsen, J. and M. B. Nielson, “Catalytic Reforming”, Brit.
Chem. Eng. 15(1 I), 1433-1436 (1970).
A = pre-exponential factor, variable dimensions Jenkins, J. H. and T. W. Stephens, “Kinetics of Cat Reforming”,
C = coke content, kg coke/kg cat Hydrocarbon Proc. 59(Nov.), 163-1 67 ( I 980).
CPj = heat capacity ofjth component, Jlmo1.K Kmak, W. S. and A. N. Stuckey, “Powerforming Process Studies
cd4 = aromatics yield for the carbon number n,% masdmass with a Kinetic Simulation Model”, AIChE National Meeting,
on feed New Orleans, Paper No. 56a, (March 1973).
E = activation energy, J/mol Krane, H. G., A. B.Groh, B. D.Schulman and J. H.Sinfelt,
EOR = end of run “Reactions in Catalytic Reforming of Naphthas”, in “Proc. Fifth
F: = flow rate of ith component. Kmolh World Petroleum Congress”, New York, 3, Section 1 1 I, Paper 4
F’TCP = (PjCp.),, - (1959), pp.39-5 1.
GY = gas yiefd (% masdmass on feed) Marin, G. B. and G. F. Froment, “Reforming of C6 Hydrocarbons
ki = k t e constant, variable dimensions on a Pt-A1203 Catalyst”, Chem. Eng. Sci. 37, 759-773 ( 1 982).
K = equilibrium constant, variable dimensions Ramage, M. P., K. R. Graziani and F. J. Krumbeck, “Development
LY = liquid yield, % mass/mass on feed of Mobil’s Kinetic reforming Model”, Chem. Eng. Sci. 35,
hT = feed flow rate, kmovh 4 1 4 8 (1980).
p = partial pressure, kPa Ramage, M. P., K. R. Graziani, P. H. Schipper, F. J.Krambeck and
n = rate of reaction, kmol/(h. kg cat) B. C. Choi, “KINTPTR (Mobil’s Kinetic Reforming Model): A
R = gas constant, 8.314 kJ/mol.K Review of Mobil’s Industrial Process Modelling Philosophy”,
Ri = ith reactor Adv. Chem. Eng. 13, 193-266 (1987).
SOR =startofrun Smith, R. B., “Kinetic Analysis of Naphtha Reforming with
t = time on stream, h Platinum Catalyst”, Chem. Eng. Prog. 55(6), 76-80 (1 959).
7‘ = inlet temperature, K Turpin, Lee E., “Modelling Commercial Reformers”, in “Catalytic
TA = total aromatics Naphtha Reforming (Science & Technology)”, J. A. George, A.
X-, = conversion by reaction i for the carbon number n, M. Aitani and J. M. Parera, Eds., Marcel Dekker, New York
kmovkmol feed (1993, pp. 437-482.
Van Trimpont, P. A., G. B. Marin and G. F. Froment, “Reforming
Greek letters of C7 Hydrocarbons on a Sulfided Commercial WA1203
Catalyst”, Ind. Eng. Chem. Res. 27, 5 1-57 (1988).
a = deactivation constant Voorhies, A., “C Formation in Catalytic Cracking”, Ind. Eng.
AH = heat of reaction, kJ/mol Chem. 37,3 18-322 (1 945).
AT = temperature drop across the reactor, K Wolf, E. E. and E. E. Peterson, “Kinetics of Deactivation of a
6 = kg catalyst/(kg molh) Reforming Catalyst During Methylcyclohexane Dehydrogenation
0 = deactivation function in a Diffusion Reactor”, J. Catal. 46, 190-203 ( I 977).
Wolff, A. and J. Kramaraz, “Kinetic Models of Catalytic
References Reforming” (Translation), Khimiya i Technologiya Topliv i
Masel, No. 12(Dec.), I@-16 (1979).
API 44 Tables, Selected Values of Properties of Hydrocarbons and Zhorov, Y. M., G. M-Panchenkov, S. P. Zel’tser and Y. A.
Related Compounds, Research Project, Thermodynamic Tirakyan, “Mathematical Description of Platforming for
Research Cent., Texas A & M Univ., College Station, TX, V Optimization of a Process (I)”, Kineetika i Kataliz, 6(6),
(1 975). 1092-1098 in Russian, English abstract in Chem. Abstr. 64,
Beltramini, J. N., T. J. Wessel and R. Datta, “Kinetics of 6358 (1 965).
Deactivation of Bifunctional WA1203-CI Catalysts by Coking”, Zhorov, Y. M., G. M.Panchenkov and I. Y. Shapiro, “Mathematical
AIChE J. 37,845-854 (1991). Description of Platforming Carried out Under Severe
Bommannan, D., R. D.Srivastava and D. N. Saraf,”Modelling of Conditions” Khim. Technol. Topl. Masel, 15 (1 1 ) 3 7 4 0 (1970).
Catalytic Naphtha Reformers”, Can. J. Chem. Eng. 67 (3) Zhorov, Y. M., Y. N. Kartashev, G. M. Panchenkov and G. M.
40-1 1 (1989). Tatarintseva, “Mathematical Model of Platforming under
Chao, K. C. and J. D. Seader, “A General Correlation of Vapor- Stationary Conditions with Allowance for Isomerization
Liquid Equilibria in Hydrocarbon Mixtures”, AIChE J. 7, Reactions” (Translation), Khimiya i Tekhnologiya Tophilv i
59MO5 (1961). Masel, No. 7(July), 9-12 (1 980).
De Pauw, R. P. and G. F.Froment, “Deactivation of a Platinum
Reforming Catalyst in Tubular Reactor”, Chem. Eng. Sci. 30
7 8 M O 1 (1 975).
Froment, G. F. and K. B. Bischoff, “Non Steady State Behavior of
Fixed Bed Catalytic Reactors Due to Catalyst Fouling”, Chem.
Eng. Sci. 16, 189-201 (1961).
Froment, G. F. and K. B. Bischoff, “Chemical Reactor Analysis
and Design”, John Wiley & Sons, New York (1979), pp. Manuscript received May I, 1996; revised manuscript received
284-296. August 5, 1997; accepted for publication August 6, 1997.

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