HUNGARIAN JOURNAL

OF INDUSTRIAL CHEMISTRY
VESZPRÉM
Vol. 39(1) pp. 117-120 (2011)

INVESTIGATION OF KINETICS OF HYDROISOMERIZATION OF

C5/C6 AND C6/C7 ALKANES AND THEIR BINARY MIXTURES

ZS. SZOBOSZLAI , J. HANCSÓK

University of Pannonia, Department of MOL Hydrocarbon and Coal Processing

8200, Veszprém Egyetem u. 10, HUNGARY

E-mail: szzsolt@almos.uni-pannon.hu

Modern gasoline quality requirements globally became stricter. These specifications parallel with the applied developments
of vehicle technologies contributing to the cleaner environment. Nowadays only the concentration of cyclo- and isoparaffins
are not limited in gasoline, because they burn cleaner, have high octane number, lower sensibility and better combustion
properties than aromatic or olefinic hydrocarbons. In the last decade because of the applied refinery investments both sulfur
and aromatic content of gasolines decreased, but the octane mass of the gasoline pool significantly decreased against the
increment of octane number requirement of spark ignition engines. Importance of isomerization of light paraffins has
been publicized in many papers. However few of them investigated, studied and explained the individual hydrocarbons
(C5/C6/C7) interaction with each other in multicomponent mixtures practically in similar to industrial hydrocarbon
feedstocks. Binary and multicomponent hydrocarbon mixture investigations can contribute to the understanding the results of
isomerization of real, feedstocks from multiple sources; which contain higher boiling point hydrocarbons (cycloparaffins,
benzene, and heptanes). Further these results can help to operate with higher flexibility, safety and economically a light
naphtha isomerization units. The hydroisomerization of n-pentane (n-C5), n-hexane (n-C6), cyclohexane (c-C6) and n-heptane
(n-C7) and their binary mixture were studied on Pt/sulfated zirconia catalyst at temperature 150–170 °C, total pressure
20 bar, 1:1 H2-hydrocarbon molar ratio. The apparent activation energies of all individual components, further the reaction
rates individually and in different composition binary mixtures were specified. Results of our experiments concluded that
the rate of reaction of the higher carbon number hydrocarbon or in case of the same carbon number the cycloparaffins (lower
volatility component) increased with increasing the concentration in the binary mixtures, while the rate of reaction of higher
volatility component decreasing.

Keywords: Isomerization, light naphtha

Introduction

Nowadays the fractions rich in isoparaffin are the most

important blending components of the gasolines because
they have high octane number, low sensibility, they are
practically free from sulphur, olefin, and aromatics, they
have low toxicity, and undesired molecules are not
generated under controlled combustion [1-4]. The
continuous demands for the application of isoparaffin
rich hydrocarbon fractions are the followings:
From 2000
– Low benzene and decreased aromatic concentration
(research octane number and octane number distribution) Figure 1: Constructed refinery investments in the EU
– Reducing the research octane number give away for high quality gasoline production until 2005
– Supplementation of the octane number decrease of the to fulfill the 2005 gasoline regulations
deep desulphurization of cracked naphthas
– Regulation of the application of MTBE The simultaneous reduction of the sulphur and
– Balancing the boiling range shifting in case of heavier aromatic content significantly decreased the octane number
ether (ETBE, TAME) application in high concentration of the gasoline pool against the increasing octane number
From 2005 requirements of the Otto engines (higher compression
– Further deep desulphurization ratio → higher octane number → higher volumetric
– Further reduced aromatic and benzene content efficiency and specific power with lower emission).
118
The importance of isoparaffin rich fractions is Experimental eqipment
presented in Fig. 1 which shows what the most important
investments are in the refineries to satisfy the demands
The applied catalytic system contains a 100 cm3 vertical
and meet the new specifications [1-4]. It can be clearly
reactor and every instrument which can be found in a
seen that the highest investments in the refinery were
commercial scale light naphtha isomerization unit.
the light paraffin isomerization processes (though the
The catalytic system contains a gas regulator/control
application of light paraffins was slightly reduced by the
and pretreatment system and an on-line gas chromatograph.
bioethanol blending, in spite of the significant effect of
the ethanol on the gasoline physical-chemical application
properties the etherification and alkylation capacity can
Materials
be significantly increased by taking advance of the
isomerization capacity), but the alkylation unit installation
and revamping was also important. The possible ways We applied 60cm3 of in situ dried and activated
to produce industrial economically isoparaffin rich Pt/sulphated-zirconia (extrudated, D: 1.5mm) catalyst and
fractions are the following: the empty space was filled with Raschig rings.
● The proper naphtha fraction separation to iso- and The feedstocks were analytical grade, sulphur free n-
normal paraffin fractions pentane, n-hexane, cyclohexane and n-heptane. The
● Alkylation of isobutane with C3-C5 olefins (direct concentration of components was varied between 0–100%
alkylation) (0, 25, 50, 75 and 100% theoretically) in binary mixtures.
● Dimerization of C3-C5 fractions rich in olefins The practically sulfur free hydrocarbons continuous
(indirect alkylation) after hydrogenation demoisturising was done with Linde 4A molecule sieve.
● Isomerization of C5-C7 fractions rich in n-paraffins
o Isomerization of benzene containing fractions
ƒ Two-steps → two reactors and different Catalyst and test methods
catalysts
ƒ One step The applied catalyst was Pt/sulfated-zirconia. Main
• isomerization of benzene containing properties of the catalyst were shown by Table 1.
fractions (the saturation of benzene and
isomerization of the n-paraffins is done in Table 1: The main characteristics of applied catalysts
the same reactor and on the catalyst) [5-6]
• in the same reactor with segmented beds Properties Values
with different catalysts [4] Pt-content, % 0.415
Pt-dispersion, % 69
The specifications of the benzene concentration of Acidity, mmolNH3/g 0.56
the naphtha fraction can be ensured by adequate pre- and Sametalic (metal (Pt) surface on the catalyst),
25.91
post-treating so the feed of reformation does not contain m2/g metal
2
benzene precursor or after the reformation they have to Smetal (specific metal surface), m metal/g cat. 0.108
be fractionated (if the reformation is gasoline purpose) APS (average particle size of the metal), nm 2.0
from the product and saturated in the isomerization plant. Specific acidity, mmolNH3/m2 cat. 0.0043
The feedstock of both of the etherification and BET surface, m2/g 130
alkylation technologies are the C4-C5 isoparaffins Microporous surface, m2/g 12.2
consequently the light paraffin isomerization will be Microporous volume, cm3/g 0.0045
one of the key processes just partly producing internal Mezoporous volume, cm3/g 0.2874
components/feeds for other technologies. Mezo-/microporous volume ratio 63.9
Average pore size, nm(Å) 8.5(85)
Experimental
Standard measurements methods were used. Pt content
of the catalyst was measured by UOP-274 standard.
Aim of our experimental work was the investigation of BET surface area and total acidity of the catalyst was
isomerization of hydrocarbons with different volatility measured by NH3 sorption according to ASTM D3663 and
and their binary mixtures. We investigated that the D4824 standards, while pore size distribution and pore
isomerization effects/rate on each other further how volume was measured by mercury intrusion porosimetry
influenced the individual hydrocarbon the other in method according to ASTM D4284 and D6761 standards
laboratory scale reactor on steady state activity catalyst. respectively. The feeds and products composition was
The inspiration of this research work was the absent of measured with gas chromatograph according to ASTM-
large scale, long term catalytic studies with near D5134 standard.
industrially parameters [7-14]. The sulphur content of all feeds and products
(GREENLAB Ltd./Analytik-Jena - Multi EA 3100-type
device) with EN ISO 20846 (2003), water content
(GREENLAB Ltd./KEM - MKA-610-type device) with
ISO 12937:2001 standard was determined.
 119
Process parameters becomes higher and near the equilibrium concentration
(cyclohexane↔methylcyclopentane) the cracking reaction
come to front that ascribe to methylcyclopentane. In the
Experiments were measured on steady state activity
examination of the gas phase composition it was
catalyst. Based on preliminary results the experiments
observed that the C2/C4 molar ratio was very low so the
was taken on 20 bar total pressure, 1.0–4.0 LHSVs,
isomerization and cracking reaction probably to take
H2/HC molar ratio was 1.0:1.0. Fine changes of the
place through C12-C8 intermediate products.
parameter combination kept measuring where the low
conversion rates (5–15%) of the individual hydrocarbon
were not inhibited by the products. 20

Reaction rate, 10-8 mol/s.gcat.

reaction rate of n-hexane
Results and discussion 15 reaction rate of n-pentane

Near low conversion rates the individual hydrocarbons 10

initial reaction rates were measured then the logarithmized
values were presented versus the inverse of temperature. 5
These methods were applied to determine the apparent
activation energies of hydrocarbons. Based on the given
data they had relatively high deviation, and these values 0
can be given with relatively high inaccuracy. Our values 0 20 40 60 80 100
and the publicized values are relevated well (Table 2) but n-pentane concentration in binary mixture, %
the most of them were determined in different catalytic
Figure 2: Changes in reaction rate of individual
system and with different parameter combinations [11-15].
components in the binary mixture
For example in case of the cyclohexane the measured
(T: 150 °C, LHSV: 1.5 h-1, P: 20 bar)
values are well correlated with publicized data
(100–150 kJ/mol).
35
Table 2: The apparent activation energies of individual
Reaction rate, 10-8 mol/s.gcat.

30
hydrocarbons reaction rate of n‐heptane
25
reaction rate of n‐hexane
Hydrocarbon n-pentane n-hexane n-heptane cyclo- 20
hexane
15
Eapparent, 10
measured 130–170 99–107 149–163 113–146
5
values, kJ/mol
0
Eapparent,
0 20 40 60 80 100
publicized 145–153 120 109–135 100–150
n-heptane concentration in binary mixture, %
values, kJ/mol
Figure 3: Changes in reaction rate of individual
The targeted quantity was added to n-hexane and components in the binary mixture
above 20% concentration it caused significantly lower (T: 150 °C, LHSV: 1.5 h-1, P: 20 bar)
reaction rate. So the reaction rate of the main
component decreased causing lower effectiveness under
80
isomerization consequently the adequate composition of
Reaction rate, 10-8mol/s.gcat.

the feed(s) has to be kept assured! 70

reaction rate of cyclohexane 
Based on our measurement the reactivity of 60
reaction rate of n‐hexane
the individual hydrocarbons were the following: 50

c-C6>n-C7>n-C6>n-C5, the main cause was that the 40

adsorption energies of cycloparaffins is higher than the 30

same carbon number linear paraffins on strongly acidic 20

catalysts so in their mixtures increasing the individual 10
component reaction rate change with different degree 0
with the concentration interdependently (Fig. 2-4). In the 0 20 40 60 80 100
hexane the other component concentration more than cyclohexane concentration in binary mixture, %
20–30% the n-hexane reaction rate was approximately
halved and its component reaction rate was Figure 4.: Changes in reaction rate of individual
comparable/similar to the other individual component components in the binary mixture
reaction rate. In case of cycloparaffin isomerization the (T: 150 °C, LHSV: 1.5 h-1, P: 20bar)
lower H2 pressure was beneficial though it increased the
selectivity of ring opening reaction. On stricter parameter
combinations the ring isomerization selectivity
120
Conclusions 6. ZS. SZOBOSZLAI, J. HANCSÓK, SZ. MAGYAR:
Upgrading of Benzene Containing Hexane Feeds by
Simultaneous Isomerization at Low Temperature and
The individual component reaction rates were lower in
Saturation of Benzene, 6th International Colloquium,
every case than in their binary mixtures. The reaction
Fuels 2007, Germany, Esslingen, 2007, In Proceedings
rates were significantly decreased in the mixtures with
(ISBN 3-924813-67-1), 293–302
increasing the concentration of individual paraffin
hydrocarbons. 7. G. D. YADAV, J. J. NAIR: Sulfated zirconia and its
Based on the measured and calculated values it was modified versions as promising catalysts for industrial
concluded that in case of the non-adequate feed or in processes, Microporous and Mesoporous Materials
case of non-adapted isomerization catalyst – where 33, (1999), 1–48
accordingly to the demands the changes of process 8. J. M. SERRA, A. CHICA, A. CORMA: Development of a
parameters have not indicated any opportunity – influence low temperature light paraffin isomerization catalysts
of some component on the isomerization efficiency with improved resistance to water and sulphur by
become significant degree hereby the main linear chain combinatorial methods, Applied Catalysis A: General,
components with low octane number reactions rate of 239(1-2), (2003), 35–42
isomerization was interfered. 9. W. TAKEMI, M. HIROMI: Reaction of linear,
branched, and cyclic alkanes catalyzed by Brönsted
ACKNOWLEDGMENT and Lewis acids on H-mordenite, H-beta, and
sulfated zirconia. Journal of Molecular Catalysis A.
We acknowledge the financial support of this work by 239, (2005), 32–40
the Hungarian State and the European Union under the
10. J. C. DUCHET, D. GUILLAUME, A. MONNIER, C.
TAMOP-4.2.1/B-09/1/KONV-2010-0003 project.
DUJARDIN, J. P. GILSON, J. VAN GESTEL, G. SZABO,
P. NASCIMENTO: Isomerization of n-Hexane over
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