Chemical Engineering Science 60 (2005) 4119 – 4129

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Kinetics of n-dodecane dehydrogenation on promoted platinum catalyst

G. Padmavathia , K.K. Chaudhuria,∗ , D. Rajeshwerb , G. Sreenivasa Raob , K.R. Krishnamurthyb ,
P.C. Trivedic , K.K. Hathic , N. Subramanyamc
a Chemical Engineering Division, Research Centre, Indian Petrochemicals Corporation Limited, Baroda-391 346, India
b Catalysis Division, Research Centre, Indian Petrochemicals Corporation Limited, Baroda-391 346, India
c Chemical Engineering Department, Faculty of Technology, MS University of Baroda, Baroda-390 002, India

Received 1 April 2004; received in revised form 4 January 2005; accepted 21 January 2005
Available online 15 April 2005

Abstract
Kinetics of n-dodecane dehydrogenation over a promoted Pt–Sn–/Al2 O3 catalyst between 733 and 763 K were determined. The reaction
scheme includes three consecutive dehydrogenation reactions and also cracking of olefins to light paraffins. Various rate models based
on Langmuir–Hinshelwood–Hougen–Watson (LHHW) and Eley Rideal mechanisms were derived for the three dehydrogenation reactions
and subjected to model discrimination and parameter estimation by using Box’s complex optimisation method. Of the 12 different models
tested, model based on LHHW mechanism with surface reaction as rate-determining step fitted the experimental data well. The estimated
rate constants of the best model are thermodynamically sound and statistically consistent.
䉷 2005 Elsevier Ltd. All rights reserved.

Keywords: Kinetics; Dehydrogenation; n-dodecane; Surface reaction; Mono olefin

1. Introduction Literature on kinetics of higher paraffin dehydrogenation

Selective dehydrogenation of higher paraffins (C10 –C14 )
to the corresponding mono olefins on promoted Pt/alumina
catalyst is an industrially important process and a key step in
the manufacture of bio-degradable detergents. The reaction
is carried out in a radial flow fixed bed reactor at higher tem-
perature (723–773 K) and low pressure (200–300 kPa) envi-
ronment, with hydrogen as diluent. The catalyst employed is
highly selective to mono olefins by major dehydrogenation
reaction. However, small amounts of di-olefins and aromat-
ics are formed by subsequent secondary dehydrogenation
reactions. All these products can lead to the formation of
light paraffins by cracking. Isomerization reaction may also
be possible. Studies on kinetics help to develop the reaction
mechanism and establish reaction network of the process
and kinetic model for simulation and design of commercial
reactors. The kinetics studies also help to evaluate catalyst
efficiency and attempt improvements thereof.
∗ Corresponding author. Tel.: +91 265 3062255.
E-mail address: kumar.chaudhari@ipcl.co.in (K.K. Chaudhuri).
is very limited. Studies by Krylova et al. (1980a) was based
on H2 –D2 exchange and dehydrogenation of n-decane and
decene for Pt/Al2 O3 and other promoted systems. Step-
wise dehydrogenation involving desorption of olefins and
di-olefins as the rate determining step was proposed by
Krylova et al. (1980b). However no mechanistic models
were tested. Initially the rate expressions were derived for
Pt–Li–W/Al2 O3 catalyst and later extended to Pt–Sn/Al2 O3
catalyst as well (Sadykhova et al., 1981). It has been es-
tablished that relative to mono metallic Pt/Al2 O3 catalyst,
bi metallic Pt–Sn/Al2 O3 promotes desorption of olefins
and hence may follow a different mechanism (Sadykhova
et al., 1984). Kinetic study of coke formation in dehydro-
genation of n-decane on Pt–Al2 O3 catalyst was reported by
Mart’yanaova et al. (1982). George (1991) studied the kinet-
ics of n-dodecane dehydrogenation on Pt–Sn/Al2 O3 catalyst
but their study was limited to lower conversions and ig-
nored the secondary dehydrogenation reactions. Taskar and
Riggs (1997) modelled a detailed kinetic scheme involv-
ing 35 pseudo components connected by a network of 36

0009-2509/$ - see front matter 䉷 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2005.01.039
4120 G. Padmavathi et al. / Chemical Engineering Science 60 (2005) 4119 – 4129
Fig. 1. Schematic diagram of the experimental set-up.
reactions covering dehydrogenation of naphthenes, isomer-
ization of paraffins, hydro cracking of single branched and
multiple branched paraffins, dehydrocyclization reactions in
the C5 –C10 range using Langmuir–Hinshelwood type reac-
tion rate expressions. Basrur et al. (1998) studied dehydro-
genation of n-decane on promoted Pt–alumina catalyst us-
ing Box–Wilson experimental design and derived quadratic
response surface correlations for predicting paraffin conver-
sion and olefins selectivity for optimisation of process con-
ditions. Zaera (2002) provided an overview of the advances
in the understanding of the reaction mechanisms of hydro-
carbon reforming processes. Emphasis was on the knowl-
edge developed by using model single crystal metals and
modern surface analytical techniques. Liu et al. (2002) de-
veloped a lumped reaction network and corresponding ki-
netics model for n-heptane reforming over an unsulfided
Pt–Re/Al2 O3 . They coupled the kinetics model with cata-
lyst deactivation kinetics which provided a powerful tool
for a priori predictions of the evolution of catalyst coke
profiles and product compositions as a function of time
on stream. Pacheco et al. (2003) studied the kinetics of
iso-octane reforming on ceria-oxide catalyst impregnated
with platinum and derived the reaction kinetics and reaction
scheme using LHHW formulation to account for the ad-
sorption of products and reactants on the active sites of the
catalyst.
This paper gives the results of kinetics of n-dodecane
dehydrogenation on a commercial catalyst based on pro-
moted Pt–Sn/Al2 O3 . While the earlier studies (George,
1991; Basrur et al., 1998) were carried out in once through
mode, the present study was in hydrogen gas recycle mode,
closer to industrial operation. Various rate models based on
Langmuir–Hinshelwood–Hougen–Watson and Eley Rideal
mechanisms have been derived for the three dehydrogena-
tion reactions and subjected to model discrimination and
parameter estimation.
2. Experimental
2.1. Experimental set-up
The experimental set-up is a fully automated system sup-
plied by M/s Xytel, India. The schematic diagram of the ex-
perimental set-up used is shown in Fig. 1. Major sections in
the unit are: (1) Hydrogen flow control module (2) Liquid
pumping system (3) Preheater and mixer for hydrogen and
n-dodecane (4) Reactor (5) Condenser and gas–liquid sepa-
rator (6) Gas recirculation module (7) Adequate flow meters
to account material balance. The reactor is a down flow of
homogenised hydrogen and n-dodecane vapour fixed bed re-
actor. Re-circulation of hydrogen is by gas compressor. The
inner diameter of the SS-321 reactor tube is 1.4 cm. Space
above and below the catalyst in the reactor was filled with
inert alumina to ensure proper distribution of fluid flow. The
total bed height including catalyst and inert alumina with an
average particle size of 0.5 mm measures to 3.6 cm. The ther-
mocouples for temperature control were placed between the
outer surface of the inner tube and inner surface of the fur-
nace. The thermocouple for bed temperature indication was
inserted at the centre of the catalyst bed. One thermocou-
ple was inserted at the end of the bed to measure the outlet
temperature. The wall effects, channelling, and nonunifor-
mity of the catalyst dispersion are common problems in
 G. Padmavathi et al. / Chemical Engineering Science 60 (2005) 4119 – 4129
laboratory reactors. The channelling and heat transfer ef-
fects at reactor wall can be neglected as the radial aspect
ratio (bed diameter to catalyst particle diameter) is > 15
(Chu and Ng, 1989). The axial aspect ratio i.e. the ratio
of catalyst bed length to catalyst particle diameter is > 30
and hence the dispersion effects can be neglected (Carberry,
1976). The catalyst bed dilution with inert particles of the
same size allowed uniform dispersion of the catalyst parti-
cles. Accurate mass flow controllers measured amounts of
hydrogen in to and out of system. Feed to reactor and prod-
uct from reactor are measured accurately up to second dec-
imal by electronic balances.
2.2. Materials
’ The n-dodecane feed was supplied by M/s. S.D. Fine
Chemicals, India and its purity is 98.63 wt% and aromat-
ics content is 0.122%. M/s Inox Air Products Ltd supplied
the hydrogen gas with the trade name INOX-II and its pu-
rity is 99.99%. The diluent, alpha-alumina was supplied by
M/s Hoechst Cerametec, inertness of diluents is checked by
extent of isomerization activity.
2.3. Preparation of catalyst
The dehydrogenation catalyst prepared according to US
Pat. 5677260 by Dongara et al. (1997) consists of highly
porous spheroidal gamma alumina support containing 0.4
wt% of platinum, 0.5 wt% of tin, 0.4wt% of indium, 0.2wt%
of iron, 0.6wt% of lithium and less than 0.1wt% of chlo-
ride. Analysis of the final catalyst sample has been car-
ried out by inductive coupled plasma (ICP) technique. Pre-
formed alumina support consists of pure alumina with
as
dominating phase, BET surface area of 160 m2 /g and bulk
density is 0.27–0.33 g/cm3 . Surface area measurements are
carried out using Sorptomatic-1900 unit by M/s Carloerba,
Italy that works on nitrogen adsorption at liquid nitrogen
temperature.
On the pre-formed alumina support, as the first step, Li
was impregnated using an aqueous solution of LiNO3 and
incipient technique, dried at 120 ◦ C for 12 h and calcined
at 600 ◦ C for 4 h in dry air. In a subsequent second step,
Pt, Sn, Fe and In were impregnated in a solution contain-
ing H2 PtCl6 , SnCl2 , Fe[NO3 ]3, In[NO3 ]3 and 10 wt% HCl.
The above conditions were favourable for the formation of
a complex between Pt and Sn and also ensure uniform dis-
tribution of active metal. The impregnated support was once
again dried at 120 ◦ C for 12 h and calcined at 550 ◦ C. In
order to reduce the chloride content to 0.1wt%, which is
responsible for side reactions, the sample is subjected to
a de-halogenation step using 5% aqueous ammonia extrac-
tion technique. Resultant sample is further calcined in dry
air at 500 ◦ C and reduced in hydrogen at 480 ◦ C for 4 h un-
der moisture free conditions at controlled temperature incre-
ments of 3 ◦ C/min rate.
4121
2.4. Experimental procedure
The reactor is first heated in a hydrogen flow of 15 l/min
at about 1 K/min to 423 K to desorb the adsorbed moisture
if any and then to 753 K at the rate of 10 K/min to enable
reduction of platinum for 4 h. Fresh n-dodecane from stor-
age tank is pumped by HPLC grade high precision metering
pump without any pulsation in to the vaporizer (pre heater).
The feed is combined with recycle hydrogen from recycle
gas compressor discharge. The desired hydrogen to hydro-
carbon ratio is maintained before the combined mixture is
sent to the pre heater, which is maintained at 573 K. The
vapourizer is designed to mix n-dodecane vapours and hy-
drogen homogeneously. The pre-heater outlet stream enters
the reactor from the top and electrical heaters are used to
achieve the desired reaction temperature. The reactor outlet
stream is cooled in a condenser and separated in to gas and
liquid products in gas–liquid separator. The gas from the
top of the gas–liquid separator is directed to the suction of
the recycle gas compressor. The condensed liquid product
is collected at definite intervals of time.
External mass transfer resistance can be minimized by
operating at a high velocity of gases and the pore diffusion
resistance can be minimized by proper sizing of the catalyst.
Absence of external mass transfer resistance was ensured
by carrying out experiments at different mass flow rates and
keeping W/F ratio constant. The conversion at two differ-
ent liquid feed flow rate having same W/F ratio remains
almost constant which indicates that the mass transfer effect
on conversion in the given range of feed flow rate is neg-
ligible. The feed flow rate used in all experimental runs is
in the range of 10–50 ml/h. Preliminary runs were carried
out to find out the particle size that allows neglecting in-
ternal transport limitation. Experiments were carried out by
varying particle size and keeping W/F ratio constant. The
results did not show any significant deviation in conversion,
which indicates the absence of intra particle diffusion.
Kinetic runs were carried out at different weight hourly
space velocity, WHSV, H2 /HC ratio at three different tem-
peratures of 733, 748 and 763 K. The WHSV is varied in the
range of 25–150. The H2 /HC ratio is varied in the range of
1–9. The liquid and gas products were analysed using Ag-
ilent 6890 GC. Innowax-5 column of 50 m length, 0.2 mm
diameter and 0.4
m film thickness and FID detector were
used for liquid product analysis. The gases were analysed
using PLOT alumina column of 50 m length and 0.2 mm
diameter capillary column and FID detector. To ascertain
the composition, a representative sample was subjected to
GC–MS analysis as per the method published (Bhatt et al.,
1993). The five groups identified in the order of column re-
tention times are (1) C5 –C11 light ends from cracking re-
actions, (2) n-dodecane (used as the reference peak), (3)
mono olefins (five positional isomers are separated keeping
end application in view), (4) conjugated di-olefins and non
conjugated di-olefins are grouped as dienes (5) aromatics
(primarily di-substituted types).
4122
17
16
Conversion & yields, wt%
15
14
13
12
11
10
9 0
0 2 4 6
Time on stream, h
Conversion
Olefin
Dienes
Fig. 2. Effect of time on stream.
3. Experimental results
All the experiments were carried out in the absence of cat-
alyst deactivation. The conversion and selectivity of various
products are presented as a function of time in Fig. 2. The
results do not show any deactivation during the run time as
can be observed from the Fig. 2. Each experiment is carried
out with fresh catalyst to ensure same efficacy of the cata-
lyst. The data considered in the present investigation for es-
timation of kinetic parameters corresponds to 1st hour data.
The dehydrogenation catalyst deactivates with time. Hence
to get the kinetics corresponding to start of run conditions
the first hour data was considered when the catalyst was
fresh and free from deactivation. The material balance for all
the runs is in the range of 98.0–99.9%. The reproducibility
of the experimental results is around 99.5%.
4. Kinetic analysis
4.1. Reaction scheme
Dodecene is the desired product in n-dodecane dehydro-
genation. The liquid product of the reaction is about 99%
and rest is gas. The hydrogen purity of gas is 99.8 wt% and
the balance is light paraffins. The amount of light paraffins
in the liquid product is around 2–2.5%, which are formed
from cracking. All the products of n-dodecane dehydrogena-
tion such as, dodecene, dodecadiene, etc. and n-dodecane
itself can crack to form light paraffins. In was assumed that
the light paraffins are formed by olefins cracking. There is
a possibility of isomerization but was ignored in the present
study. In accordance with the product distribution and the
above observations the system can be described by the fol-
lowing reactions:
Dehydrogenation
Olefins formation:
k1
C12 H26 ↔ C12 H24 + H2 .
k−1
G. Padmavathi et al. / Chemical Engineering Science 60 (2005) 4119 – 4129
3 Secondary dehydrogenation
Dines formation:
2.5
2 k2
Yields, wt%
C12 H24 ↔ C12 H22 + H2 . (2)
k−2
1.5
Aromatics formation:
1
0.5 k3
C12 H22 → C12 H18 + 2H2 . (3)
8 10 Olefins cracking
k4
Aromatics C12 H24 + 2H2 → < C11 hydrocarbons. (4)
Light paraffins
Hydrogen
Five possible reaction schemes, shown in Table 1, were de-
rived for the three dehydrogenation reactions. For each of
these mechanisms several rate equations were derived de-
pending upon the assumed rate determining step. Twelve
possible rate equations were retained. The rate equations
are presented in Table 2. In Mechanism A, LHHW formal-
ism was used for formulation of kinetics of solid catalysed
reversible dehydrogenation reaction. It was reported that
though the assumptions made below may not always be ful-
filled completely it is accepted that this approach is the most
suitable and reliable way of rationalizing observed catalytic
rate data (Froment and Hosten, 1981). The reaction scheme
corresponding to the three major dehydrogenation reactions
have steps for adsorption, surface reaction and desorption
as shown in Table 1. The symbol L denotes the active site
of the catalyst surface. In step 1 molecular adsorption of n-
dodecane takes place on catalyst active site. In the second
step the adsorbed n-dodecane reacts with another active site
to form C12 H24 -L and H2 -L. In third step dodecene is des-
orbed. The olefin is readsorbed (step 4) and diene is formed
in stages 5 and 6. Dehydrogenation of diene takes place in
a similar way. All the reactions are assumed to have a step
that is slower than the other steps, i.e. rate determining step.
For example, if adsorption is considered as rate determining,
then step 1, step 5 and step 9 in Table 1 are rate determin-
ing steps. The rate equations were derived in the same way
similar to a single reaction. Rate equations were written for
the rate determining step of each of the three reactions in
terms of the concentrations of the adsorbed species. These
concentrations were then eliminated by means of the Lang-
muir equilibrium relations. This gives rate equations in terms
of accessible gas-phase partial pressures and contains a de-
nominator resulting from the adsorption of reacting species.
Since all the three reactions are assumed to take place on
the same active sites, the three rate equations have the same
denominator.
The mechanism B is dissociative dehydrogenation and
surface recombination of hydrogen. The final rate expres-
sions resulted will be same as mechanism A if it is assumed
that the surface contains adsorbed paraffins, olefins, dienes,
aromatics and hydrogen.
The mechanism C was dissociative adsorption of n-
dodecane with abstraction of one hydrogen atom in first
(1)
stage and abstraction of another hydrogen atom in second
 G. Padmavathi et al. / Chemical Engineering Science 60 (2005) 4119 – 4129 4123

Table 1 stage to form C12 H24 -L after which desorption of the olefin
Reaction schemes for n-dodecane dehydrogenation takes place in third stage. Final rate expression was derived
A. LHHW model: molecular dehydrogenation assuming that the adsorbed paraffins, olefins, dienes, and
1. C12 H26 + L ↔ C12 H26 L trines and dissociatively adsorbed hydrogen are present on
2. C12 H26 L + L ↔ C12 H24 L + H2 L the surface and the concentrations of other surface compo-
3. C12 H24 L ↔ C12 H24 + L nents are negligible.
4. C12 H24 + L ↔ C12 H24 L
5. C12 H24 L + L ↔ C12 H22 L + H2 L
Mechanism D is Eley Rideal mechanism in which one
6. C12 H22 L ↔ C12 H22 + L adsorbed species reacts with another species in the gas phase.
7. C12 H22 + L ↔ C12 H22 L Mechanism E was proposed by Biloen et al. (1977) (14)
8. C12 H22 L + L ↔ C12 H18 L + H2 + H2 L which involves: (i) cleavage of the C–H bond in dissociative
9. C12 H18 L ↔ C12 H18 + L adsorption to form an adsorbed alkyl group (ii) cleavage of
10. H2 L ↔ H2 + L
the second C–H bond resulting in - or -bonded olefin and
B. Atomic dehydrogenation and surface recombination of hydrogen (iii) desorption of the olefin.
1. C12 H26 + L ↔ C12 H26 L
2. C12 H26 L + L ↔ C12 H25 L + HL
3. C12 H25 L + L ↔ C12 H24 L + HL 5. Parameter estimation and model discrimination
4. C12 H24 L ↔ C12 H24 + L
5. C12 H24 + L ↔ C12 H24 L
6. C12 H24 L + L ↔ C12 H23 L + HL Since the reactor was operated in integral mode, parame-
7. C12 H23 L + L ↔ C12 H22 L + HL ter estimation was based on the minimization of the sum of
8. C12 H22 L ↔ C12 H22 + L the residual squares of the conversion and selectivity of the
9. C12 H22 + L ↔ C12 H22 L products by Box’s complex optimisation method. The cal-
10. C12 H22 L + L ↔ C12 H21 L + HL
culated conversion and selectivity of the products were ob-
11. C12 H21 L + L ↔ C12 H18 L + H2 + HL
12. C12 H18 L ↔ C12 H18 + L tained by numerical integration of the set of ordinary differ-
13. 2HL ↔ H2 L + L ential material balance equations of reference components.
14. H2 L ↔ H2 + L
5.1. Material balance
C. Stepwise dehydrogenation (Kipperman)
1. C12 H26 + 2L ↔ C12 H25 L + HL
2. C12 H25 L + L ↔ C12 H24 L + HL The rate of formation of each component can be expressed
3. C12 H24 L ↔ C12 H24 + L as
4. C12 H24 + 2L ↔ C12 H23 L + HL Rate of disappearance of paraffin (n-dodecane):
5. C12 H23 L + L ↔ C12 H22 L + HL
6. C12 H22 L ↔ C12 H22 + L dXP
7. C12 H22 + 2L ↔ C12 H21 L + HL = −r1 . (5)
d
8. C12 H21 L + L ↔ C12 H20 L + HL
9. C12 H20 L ↔ C12 H18 + H2 + L Rate of formation of olefins (dodecene):
10. 2HL ↔ H2 + 2L
dXO
= r1 − r2 − r4 . (6)
D. Eley Rideal mechanism d
1. C12 H26 + L ↔ C12 H26 L
2. C12 H26 L ↔ C12 H24 L + H2 Rate of formation of diene (dodecadine):
3. C12 H24 L ↔ C12 H24 + L
dXD
4. C12 H24 + L ↔ C12 H24 L = r2 − r3 . (7)
5. C12 H24 L ↔ C12 H22 L + H2 d
6. C12 H22 L ↔ C12 H22 + L
Rate of formation of aromatics:
7. C12 H22 + L ↔ C12 H22 L
8. C12 H22 L ↔ C12 H18 L + 2H2 dXA
9. C12 H18 L ↔ C12 H18 + L = r3 − r4 . (8)
d
E. Rate of formation of light paraffins (< C11 ):
1. H2 + 2L ↔ 2HL
2. HL + C12 H26 ↔ C12 H25 L + H2 dXLP
= r4 . (9)
3. C12 H25 L ↔ C12 H24 HL d
4. C12 H24 HL ↔ C12 H24 + HL
5. HL + C12 H24 ↔ C12 H23 L + H2 Rate of formation of H2 :
6. C12 H23 L ↔ C12 H22 HL
7. C12 H22 HL ↔ C12 H22 + HL
dXH2
= r1 + r2 + 2r3 − 2r4 , (10)
8. HL + C12 H22 ↔ C12 H21 L + H2 d
9. C12 H21 L ↔ C12 H20 HL
10. C12 H20 HL ↔ C12 H18 + H2 + HL
where  = W/F = g cat h/mol paraffin feed; ri (i = 1–4) is
11. HL + HL ↔ H2 + 2L rate of ith reaction. Reaction rate is expressed in terms of
partial pressure of the components. The moles of different
4124 G. Padmavathi et al. / Chemical Engineering Science 60 (2005) 4119 – 4129

Table 2
Rate equations for various rate models

Mechanism A
r1 = k1 (pP − pO pH /KE1 )/DEN (adsorption rds)
r2 = k2 (pO − pD pH /KE2 )/DEN
r3 = k3 pD /DEN
DEN = (1 + KP pO pH /KE1 + KO pD pH /KE2 + KD pA pH 2 + K p + p /K )
A A H H
r1 = k1 KP (pP − pO pH /KE1 )/DEN (surface reaction rds)
r2 = k1 KO (pO − pD pH /KE2 )/DEN
r3 = k3 KD PD /DEN
DEN = (1 + KP Pp + KO pO + KD pD + KA pA + KH pH )2
r1 = k1 KE1 (pP /pH − pO /KE1 )/DEN (desorption rds)
r2 = k2 KE2 (pO /pH − pD /KE2 )/DEN
r3 = k3 KD pD /DEN
DEN = (1 + KP pP + KE1 pP /(KO pH ) + KE2 pO /(KD pH ) + pD /(KA pH 2 ) + p /K )
H H
Mechanism C
r1 = k1 (pP − pO pH /KE1 )/DEN (adsorption rds)
r2 = k2 (pO − pD pH /KE2 )/DEN
r3 = k3 pD /DEN
1.5 /k8k9√K10 + √p /K )2
DEN = (1 + pO √ pH /K2 K3√ K10 + pD √ pH /K5 K6√ K10 + pA pH H 10
r1 = k1 (pP − pO pH /KE1 )/DEN (surface reaction rds)
r2 = k1 (pO − pD pH /KE2 )/DEN
r3 = k3 PD /DEN
√ √
DEN = pH(1 + pO /K3 + pD /K6 + pHpA /K9 + pH /K10 )2
r1 = k1 KE1 (pP − pO pH /KE1 )/DEN (desorption rds)
r2 = k2 KE2 (pO − pD pH /KE2 )/DEN
r3 = k3 KD pD /DEN
DEN = (1 + K4K5pO + K7K8pD + K10−1.5 pH 1.5 )
Mechanism D
r1 = k1 (pP − pO pH /KE1 )/DEN (adsorption rds)
r2 = k2 (pO − pD pH /KE2 )/DEN
r3 = k3 pD /DEN
DEN = (1 + KP pO pH /KE1 + KO pD pH /KE2 + KD pA pH 2 +K p )
A A
r1 = k1 KP (pP − pO pH /KE1 )/DEN (surface reaction rds)
r2 = k2 KO (pO − pD pH /KE2 )/DEN
r3 = k3 KD pD /DEN
DEN = (1 + KP pP + KO pO + KD pD + KA pA )2
r1 = k1 KE1 (pP − pO pH /KE1 )/DEN (desorption rds)
r2 = k2 KE2 (pO − pD pH /KE2 )/DEN
r3 = k3 KA pD /DEN
DEN = 1 + KP pP + KE1 pP /(KO pH ) + KE2 pO /(KD pH ) + KD pD /pH 2)
Mechanism E
r1 = k1 (pP − pO pH /KE1 )/DEN (adsorption rds)
r2 = k2 (pO − pD pH /KE2 )/DEN
r3 = k3 pD /DEN
√
DEN = (1 + K3 pO + K5 pD + K7 pA pH + K1 /pH )
Power law
r1 = k1 (pP − pO pH m1 /K )
E1
r2 = k2 (pO − pD pH /KE2 )
r3 = k 3 p D
r 4 = k 4 pO
r4 is same for all the models
KEi = ki /k−i

components present at any point when conversion of paraffin
is Xp ; moles of Paraffin 1−XP ; olefins = XO ; diene = XD ;
aromatics = XA ; light paraffins = XLP ; hydrogen = XH2 .
Partial pressure of each species can be expressed as
pP = (1 − XP )pt /T M; pO = XO pt /T M;
pD = XD pt /T M; pA = XA pt /T M;
where T M= total moles (feed rate + recycle gas flow
rate).
The above ordinary differential equations were integrated
numerically by the fourth order Runge–Kutta Method for a
given set of kinetic parameters and operating conditions to
obtain concentration of each component at the end of reactor.
The boundary conditions are

pH2 = XH2 pt /T M, (11) At  = 0; Xi = 0; i = 1 − n (n = no. of component).

 G. Padmavathi et al. / Chemical Engineering Science 60 (2005) 4119 – 4129 4125

Table 3
Results of objective function for various rate models

Type of model Rate determining step Objective Fc Ft

function

1. LHHW model Table 1 A Adsorption 7.87 2.096 43573

2. LHHW model Table 1 A Surface reaction 13.01 2.096 29350
3. LHHW model Table 1 A Desorption 16.11 2.096 28864
4. Rate model Table 1 C Adsorption 15.42 2.096 14973
5. Rate model Table 1 C Surface reaction 14.59 2.096 17893
6. Rate model Table 1 C Desorption 18.16 2.096 14449
7. Eley Rideal Table 1 D Adsorption 8.87 2.166 34924
8. Eley Rideal Table 1 D Surface reaction 14.67 2.166 28841
9. Eley Rideal model Table 1 D Desorption 15.24 2.166 28817
10. Rate model Table 1 E Adsorption 13.47 2.096 19401
11. Power-law model (m1 = 1.2) 23.80 2.557 25630
12. Power-law model at (m1 = 1; T = 733 K) 16.71 2.557 64497

The kinetic parameters were estimated by minimization of 200

the sum of the squares of the residuals of calculated and

r0, gmol/h/gcat
150
experimental values of conversion and selectivity of all the 733 K
100
components by using Box complex optimization method. 748 K

The objective function  is 50

763 K

= (Xn,m cal − Xn,m exp )2 , (12) 0
190 210 230 250 270 290
n m
Total pressure, KPa

when Xn,m cal is the predicted selectivity of species m in

the nth experiment and Xn,m exp. is experimental selectivity
value. The objective function values of all the rate models
tested are presented in Table 3.
The conditions used to discriminate between the above
described various models are: (i) if negative values were
obtained for one or several parameters, the model was re-
jected (ii) objective function value should be the least of all
the models (iii) when the objective function of two models
are same, then the model with less number of parameters is
considered. Another criteria for model discrimination is (iv)
an F -test (Sotelo et al., 1993) based on the ratio, Ft

Xi pr 2 /k
Ft =   , (13)
(Xipr − Xi exp )2 /(nm − k)
where k is number of parameters in the model, n is number
of experimental points, m is number of species. A given
regression is considered to be meaningful when Ft is larger
than Fc (k, (nm−k), ). The  value considered in the present
work is 0.05. Ft and Fc values are also presented in Table 3.
Model discrimination is done by rejecting models based
on their objective function, , values with minimum number
of experimental data. Rate models 11 and 12 based on power
law in Table 3 were rejected because of their high  values.
Then the models with maximum  value in each mechanism
of A, C & D were rejected. This, eliminated models with
desorption as rate determining step (models 3, 6, 9) in each
mechanism.
Of the remaining models, with adsorption and surface re-
action as rate determining step, the model with minimum
Fig. 3. Initial reaction rate vs. total pressure.
 value was retained for each mechanism. This retained
LHHW models 1 and 2 with adsorption and surface reaction
as rate determining step. Finally both these LHHW mod-
els with adsorption and surface reaction as rate determining
step were considered for further processing with complete
data from further experimentation that allows to check the
parametric sensitivity of the model. The final objective func-
tion value of the rate model with surface reaction as rate
determining step obtained from Eq. (12) is 296 as compared
to that of 738, for rate model with adsorption as rate de-
termining step, thereby eliminating the LHHW model with
adsorption as rate determining step.
To verify the observations further, method of initial rates
is used. Initial rate is reaction rate at extremely low con-
version of a feed containing no reaction products. The ini-
tial reaction rates, r0 , were calculated at different total pres-
sures for three different temperatures and the variation of r0
with total pressure as a function of temperature is shown in
Fig. 3. The trend from the Fig. 3 clearly indicates that sur-
face reaction is rate determining step at all the three temper-
atures (Froment and Bischoff, 1979).
The rate of reaction was calculated from the W/F vs.
conversion data. The conversion of each reaction was calcu-
lated by material balance. The data were fitted in to a smooth
logarithmic curve of the type X = m ∗ ln(W/F ) + C. Then
the equation is differentiated dX/d(W/F ) to obtain rate as
a function of W/F . The rate data indicate that the rate of
4126 G. Padmavathi et al. / Chemical Engineering Science 60 (2005) 4119 – 4129

Fig. 5. Arhenius plots of kinetic parameters.

Fig. 4. Rate vs. conversion of paraffins.

formation of aromatics is proportional to the concentration

of dienes and does not depend on the concentration of olefins
and paraffins which also supports the step wise conversion
in the order paraffin–olefin–diene–aromatics. Fig. 4 shows
the plot of rate of disappearance of n-dodecane and building
up of the desired product olefin. The rate decreased linearly
with conversion at the three temperatures. As per Tashkirova
and Kiperman (1970) the reaction is inhibited by at least one
of its products, i.e. by olefins, dienes, or aromatics, if the
rate vs. conversion curve is concave. The results show that
the desorption of the products may not be controlling the
rate in the present case which was confirmed from objective Fig. 6. Adsorption constants vs. temperature.
function values.
Based on the observations drawn from rate data and anal-
ysis of objective function values as discussed above, rate The Arhenius plot of the rate constants is given in Fig. 5.
model based on LHHW mechanism with surface reaction as Adsorption equilibrium constants decreased with increase
rate determining step was retained as final model for the pro- in temperature as it should. Hence the estimates of activa-
cess. The rate expressions according to the retained model is tion energies have to be statistically positive and those for
adsorption enthalpies negative (Froment and Hosten, 1981).
r1 = k1 KP (pP − pO pH /KE1 )/(1 + KP pP The plot of adsorption constants vs. 1/T is given in Fig. 6.
+ KO pO + KD pD + KA pA + KH pH )2 , (14) The activation energy and pre-exponential factor values of
the retained model for all the reactions are in the same range
r2 = k2 KO (pO − pD pH /KE2 )/(1 + KP pP with that reported for n-decane dehydrogenation (Krylova
+ KO pO + KD pD + KA pA + KH pH )2 , (15) et al., 1980a,b).
The values of the kinetic parameters along with standard
r3 = k3 KD pD /(1 + KP pP + KO pO + KD pD
error of kinetic coefficients are given below:
+ KA pA + KH pH )2 , (16)
k1 = 3.25 × 1015 exp(−78.0 ± 0.2/RT ) mol Pa2 /h/g,
r4 = k4 pO , (17)
k−1 = 3.65 × 103 exp(29.5 ± 0.0001/RT ) mol Pa/h/g,
where KP , KO , KH , KD , KA are adsorption equilibrium
constants and are related to the equilibrium constants of the k2 = 8.60 × 1015 exp(−81.9 ± 0.021/RT ) mol Pa2 /h/g,
steps of the reaction in the following way:
k−2 = 1.28 × 103 exp(38.8 ± 0.22/RT ) mol Pa/h/g,
KP = K1 ; KO = 1/K3 ; KD = 1/K6 ;
k3 = 2.49 × 1018 exp(−111.2 ± 0.12/RT ) mol Pa2 /h/g,
KA = 1/K9 ; KH = 1/K10 . (18)
k4 = 3.55 × 1013 exp(−288.4 ± 3.2/RT ) mol Pa−1 /h/g,
The rate coefficients ki obeyed the Arhenius temperature
dependence KP = 2.78 × 102 exp(25.4 ± 0.061/RT ) Pa,

ki = A exp(−E/RT ). (19) KO = 3.80 exp(61.3 ± 0.34/RT ) Pa,

 G. Padmavathi et al. / Chemical Engineering Science 60 (2005) 4119 – 4129 4127

Fig. 9. Effect of H2 /HC ratio on conversion and selectivity of products.

Fig. 7. Effect of W/F on conversion.

100 50

Conversion, %
80 Olefin 40
Selectivity, %
60 30
T= 733 K
40 20
Conversion
20 10
0 Diene 0
0 5 10 15 20
Run number ____ : Pred
Symbol: Expt.

100 50

Conversion, %
80 Olefins 40
Selectivity, %

60 30
T = 748K
40 Conversion 20

20 10
Dienes
0 0
0 5 10 15 20
Fig. 8. Effect of W/F on selectivity of olefins. Run number ______ Pred
Symbol: Expt.

KH = 3.04 × 102 exp(25.2 ± 0.1/RT ) Pa, 100 50

T = 763 K Olefins

Conversion, %
80 40
Selectivity, %

KD = 7.6 exp(78.3 ± 0.48/RT ) Pa,

60 Conversion 30
KA = 8.2 exp(78.0 ± 3.06/RT ) Pa. 40 20

20 Dienes 10

6. Effect of operating parameters
Figs. 7 and 8 show the effect of W/F on conversion and
selectivity of mono olefins at three different temperatures. At
constant W/F paraffin conversion increased with increase in
reaction temperature. The selectivity of mono olefin and di-
ene decreased with increase in temperature. The decrease in
selectivity of mono olefins with increase in conversion, sup-
ports the stepwise mechanism of the paraffin dehydrogena-
tion reaction (Kiperman, 1975, 1977). The loss of olefins
selectivity is due to secondary dehydrogenation to diene and
then to aromatics and parallel formation of light paraffins
by olefin cracking and finally to coke. The selectivity of
aromatics and light paraffins increases with increase in tem-
0 0
0 5 10 15 20
Run number ______ Pred
Symbol: Expt.
Fig. 10. Comparison of predicted conversion and selectivity with experi-
mental values.
perature. The effect of H2 /HC ratio on paraffin conversion
and selectivity of the products is shown in Fig. 9. The paraf-
fin conversion decreased with increase in H2 /HC ratio. The
decreased H2 /HC ratio at a constant pressure lowers the hy-
drogen partial pressure, which favors higher conversion.
Fig. 10 shows the comparison of model predicted con-
version and selectivity of olefins and dienes with that of
4128 G. Padmavathi et al. / Chemical Engineering Science 60 (2005) 4119 – 4129

experimental values at three temperatures for different runs D diene

with different operating conditions, which included the ef- A aromatics
fect of WHSV, H2 /HC ratio and temperature. The agreement LE light ends
between the predicted and experimental values is good as
shown in the Fig. 10.
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