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Light Naphtha Isomerization Process: A Review

G. Valavarasu & B. Sairam

To cite this article: G. Valavarasu & B. Sairam (2013) Light Naphtha Isomerization Process: A
Review, Petroleum Science and Technology, 31:6, 580-595, DOI: 10.1080/10916466.2010.504931

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Petroleum Science and Technology, 31:580–595, 2013
Copyright © Taylor & Francis Group, LLC
ISSN: 1091-6466 print/1532-2459 online
DOI: 10.1080/10916466.2010.504931

Light Naphtha Isomerization Process: A Review

G. Valavarasu1 and B. Sairam2

1
Corporate R&D Centre, Hindustan Petroleum Corporation Limited, Bangalore, India
2
R&D Centre, Chennai Petroleum Corporation Limited, Chennai, India

The isomerization process is gaining importance in the present refining context due to limitations
on gasoline benzene, aromatics, and olefin contents. The isomerization process upgrades the octane
number of light naphtha fractions and also simultaneously reduces benzene content by saturation
of the benzene fraction. Isomerization complements catalytic reforming process in upgrading the
octane number of refinery naphtha streams. Isomerization is a simple and cost-effective process for
octane enhancement compared with other octane-improving processes. Isomerate product contains
very low sulfur and benzene, making it ideal blending component in refinery gasoline pool. Due to the
significance of isomerization to the modern refining industry, it becomes essential to review the process
with respect to catalysts, catalyst poisons, reactions, thermodynamics, and process developments.
The present research thrust in this field along with future scope of work is also discussed briefly.
The isomerization process is compared with another well-known refinery process called the catalytic
reforming process.

Keywords: catalyst poisons, isomerization catalysts, isomerization process, light naphtha

INTRODUCTION

Isomerization to upgrade the octane number of light naphtha streams has been known to the
refining industry for many years (Cusher, 1986a, 1986b). Isomerization was developed during
World War II to produce isobutane necessary for the manufacture of alkylates, which are used
as blendstocks in high-octane aviation gasoline. Today isomerization is mainly focused on the
upgrading of refinery C5 /C6 naphtha streams into high-octane motor gasoline (Newalkar et al.,
2005). Isomerization of light naphtha streams rich in C5 s and C6 s typically results in an increase
of 10–20 octane numbers (Weyda and Kohler, 2002).
The isomerization process gained significance in refining industry only after the phasing out
of lead from gasoline in many countries. Worldwide there is a trend toward improving the quality
of fuels to decrease the impact of environmental and health effects. Limitations are imposed on
gasoline benzene, aromatics, and olefin contents. Since aromatics and olefins are the high-octane
components, limiting their concentration in gasoline will lead to decrease in octane number apart
from reduced gasoline production. The octane number was compensated by the addition of high

Address correspondence to G. Valavarasu, Senior Manager (Corporate R&D), Hindustan Petroleum Corporation
Limited, Whitefield, Banglore 560066 India. E-mail: [email protected]

580
 LIGHT NAPHTHA ISOMERIZATION PROCESS 581

octane oxygenates in gasoline pool. Ground water contamination in underground storage tanks
led to phasing out of these components from gasoline blending. Phasing out limitations on high-
octane gasoline components resulted in octane reduction from the refinery gasoline pool. In this
global scenario, isomerization of light naphtha is gaining popularity as an octane provider for the
gasoline pool since it produces highly branched alkanes, which have high octane numbers and
low vapor pressures.
Initially isomerization units produced isobutane from n-butane using aluminum chloride for
acidic function in Friedel-Crafts-type catalyst system. Dual functional isomerization catalysts
were developed later, which were effective only at high temperatures due to their low activity.
These early dual functional catalysts were limited by thermodynamic equilibrium constrain of
isomerization reactions and thus low isomer conversion was only possible. High-activity dual-
functional catalysts that work at lower temperatures were developed during 1950s. Development of
high-activity catalysts and optimized process schemes resulted in renewed interest in isomerization
technology. Isomerization units in refineries or petrochemical complexes convert low-octane C5 /C6
streams into high-octane gasoline and C4 into i-C4 for alkylation or MTBE (de Boer and Johnson).
Isomerization is a fixed-bed catalytic process conducted in vapor phase at low temperatures in
the presence of hydrogen using a metal hydrogenation catalyst on a suitable support material
promoted by the injection of small amounts of organic chloride.
Out of the other gasoline upgrading processes, isomerization becomes a significant process
due to its favorable product characteristics especially with respect to aromatics, research octane
number (RON), and olefins and low capital investment. Reforming produces aromatics, which has
a limit in gasoline pool while isomerization produces more of desired isoparaffins. The isomerate
shows low sensitivity between RON and MON as compared with similar products formed from
other processes (Leprince, 2001).
Karthikeyan et al. (2008) studied Ni-impregrated Pd/H-mordenite catalyst for isomerization
of n-decane and their study showed the effectiveness of this catalyst with respect to improved
product octane number. Liu et al. (2009) described the physicochemical and isomerization property
of Pt/SAPO-11 catalysts promoted by rare earths. Most of the literature on isomerization deals with
studies on pure model compounds on various novel catalyst systems (Sinha and Sivasanker, 1999;
Hochtl et al., 2001; Lopez et al., 2004). Funez et al. (2008) detailed about hydroisomerization in
liquid phase of a refinery naphtha stream over Pt-Ni/H-beta zeolite catalysts.
Dufresne et al. (1990) provided details concerning a mordenite catalyst for hydroisomerization
of paraffinic feeds. Del Rossi et al. (1994) discussed a process for ring opening of aromatics and
cycloaliphatics, as well as isomerization of aliphatics. Aboul-Gheit and Ghoneim (2008) discussed
in detail many patents on the catalysis and engineering of hydroisomerization and reforming
processes with emphasis on different types of catalysts. Review on industrial isomerization process
is very scarce in open literature since most of the process details are proprietary in nature. The
growing importance of this process in recent times is the reason for detailed review of this
process.

ISOMERIZATION FEEDSTOCK AND CHARACTERIZATION

Light straight run naphtha streams rich in C5 and C6 normal paraffins are the usual feeds for
the isomerization unit. Some of the other streams rich in C5 and C6 normal paraffins such as
condensate and light raffinate from aromatic extraction units are also suitable for isomerization
units. Benzene-containing feeds are also potential feeds since modern catalysts help to manage
the benzene content through saturation and ring opening reactions to high-octane product (Weyda
and Kohler, 2002). Characterization of the feedstock for the Isom unit is very critical and refiners
determine the complexity of the feed in terms of increase in X Factor, which is the sum of C6
582 G. VALAVARASU AND B. SAIRAM

TABLE 1
Important Isomerization Reactions and Their Features

Reaction Feature

Isomerization of n-paraffins  Desirable reaction and limited by equilibrium

 High-activity catalysts result in low temperature
operation and thus improve isomer yield
Ring opening of naphthenes  Favored by high temperatures and high catalyst
activity
Benzene saturation  Desirable reaction
 Occurs over hydrogenation sites of the catalyst
 Highly exothermic resulting in high reactor T
Hydrocracking  Favored by high reactor temperature
 Results in yield loss

naphthenes, benzene, and C7C in the combined feed. Normally X Factor is in the range of 15–20
for typical C5 /C6 isomerization feedstocks.

ISOMERIZATION REACTION CHEMISTRY

Isomerization reactions aim to convert linear paraffins (C4 through C6 ) into their isomers. The
important reactions that occur during isomerization are detailed in Table 1. Figure 1 shows the
important isomerization reactions along with the corresponding octane number of feed and product
hydrocarbon species.

FIGURE 1 Important isomerization reactions.

 LIGHT NAPHTHA ISOMERIZATION PROCESS 583

THERMODYNAMICS OF ISOMERIZATION REACTIONS

The isomerization reaction is equilibrium limited and slightly exothermic in nature with heat
of reaction in the range of 4 to 20 kJ/mol and thus complete conversion of n-paraffins into
isoparaffins is not achievable over isomerization catalysts. The maximum possible conversion
is a strong function of reactor temperature. Thermodynamics favors lower temperatures for n-
paraffin isomerization to achieve equilibrium concentration. Application of highly active chlorided
alumina catalysts achieves lower temperatures and higher isomer content compared to zeolite
based catalysts. Weiszmann (1986) reported an increase of isopentane content from 64 mol%
to 82 mol% by decreasing the temperature from 260ıC to 120ı C for pentane equilibrium.
Mostly the composition of reactor products closely approach equilibrium values for most of the
isomerization catalysts. Isomerization reactions are relatively slow and thus long residence times
are required for acceptable conversions. Isomerization is always accompanied by consequent
hydrocracking reaction resulting in small yield loss. Multibranched paraffins are more prone
to hydrocracking than monobranched paraffins. The products of consecutive isomerization and
hydrocracking reactions include monobranched isomers, dibranched isomers and cracked light
products. Only traces of tribranched isomers are usually observed in the products since they are
cracked rapidly (Deldari, 2005). The rates of isomerization and cracking reaction steps determine
the product distribution. It is essential to inhibit side reactions such as hydrocracking and olefin
formation during isomerization (Speight and Ozum, 2002).

ISOMERIZATION PROCESS DESCRIPTION

Figure 2 shows the typical process flow diagram of C4 isomerization unit (Occupational Safety
and Health Administration, 2008). The C5 /C6 isomerization units mostly resemble that of a
hydrotreating unit. The light straight run naphtha stream is mixed with hydrogen and heated
to reaction temperature and fed to a series of reactors. The final reactor effluent is sent to a
separator to separate excess hydrogen from the reactor product for recycling back to the reactors

FIGURE 2 Typical process flow diagram of C4 isomerization unit.

584 G. VALAVARASU AND B. SAIRAM

along with fresh make-up hydrogen. The separator bottom is then sent to a stabilizer where off-
gases are removed at the top and stabilized isomerate product is obtained from the bottom. The
debutanized isomerate product is sent for gasoline blending.

ISOMERIZATION PROCESSES BASED ON FEED

There are two types of isomerization processes based on feedstock such as butane isomerization
and C5 /C6 isomerization. C4 isomerization into isobutane is very important, because the isobutane
product is utilized as feedstock for alkylation and methyl tertiary butyl ether (MTBE) units. Butane
isomerization mainly takes place in vapor phase. C5 /C6 isomerization is applied to increase the
octane number of straight run naphtha streams. C5 /C6 isomerization mostly occurs in liquid phase
depending upon the operating conditions (Graeme and van der Laan, 2003). C5 /C6 isomerization
process consumes more hydrogen compared with C4 isomerization process due to benzene satu-
ration reactions. The catalyst for C4 isomerization can be designed using less platinum content
compared with C5 /C6 isomerization catalyst due to lower hydrogen uptake. Albamarle ( ) claims
to have developed a C4 isomerization catalyst with only half the platinum content compared to
C5 /C6 isomerization catalyst and saved huge costs (Graeme and van der Laan, 2003).

MEASUREMENT OF ISOMERIZATION UNIT PERFORMANCE

Isomerization unit performance is usually expressed in terms of the ratio between isoparaffin to
n-paraffin. For example, butane isomerization unit performance is expressed as follows (Graeme
and van der Laan, 2003):

Isobutane ratio D (isobutane in product) / (sum of isobutane & butane in product)

Butane selectivity is defined as the ratio between butanes in product to butanes in feed. For C5 /C6
isomerization units, the paraffin isomerization number (PIN) is the most widely used performance
indicator, and is defined as follows:

PIN D (isopentane in product) / (sum of C5 paraffins in product) C (2,2 dimethylbutane and

2,3 dimethylbutane in product) / (sum of C6 paraffins in product).

Albamarle reports product PIN of about 115 for one of its isomerization catalysts at higher space
velocities (Graeme and van der Laan, 2003).

PRODUCT YIELDS AND QUALITY

Once-through or single-pass isomerization results in only partial conversion of n-paraffins due to

thermodynamic equilibrium limitations of isomerization reactions. An octane increase of about 10–
13 units is only possible using single pass isomerization units even with highly active chlorided
alumina catalysts. However, recycling the unconverted n-paraffins to the reactor as in recycle
isomerization units results in an octane number increase of about 18–22 in the isomerate product.
For Union Oil Product (UOP) Butamer process, a volumetric yield of more than 100% isobutane is
reported based on the n-butane feed (Rosati, 1986). Isomerization produces a very small amount of
light gases, including hydrogen, C1 , C2 , and liquified petroleum gas (LPG) by mild hydrocracking
 LIGHT NAPHTHA ISOMERIZATION PROCESS 585

TABLE 2
Typical Operating Conditions of Different Isomerization Processes

Process Chlorinated Metal Oxide

Parameter Alumina Zeolites (Zirconia Based)

Temperature, ı C 130–150 250–280 180–210

Pressure, barg 15–35 15–35 15–35
LHSV, hr 1 1.0–3.0 1.0–3.0 1.0–3.0
H2 /HC Molar Ratio 1.0–2.0 1.0–2.0 1.0–2.0

of naphtha feedstock. Typical isomerate yields in the range of 95–98 LV% could be achieved
during isomerization process. Isomerate properties are normally measured in terms of i-C5 /n-C5
and 2,2-DMB/n-C6 ratios.

PROCESS PARAMETERS AND OPERATING CONDITIONS

The extent of n-paraffin isomerization reaction during isomerization process depends on the pro-
cess variables such as reactor temperature, operating pressure, space velocity, and H2 /hydrocarbon
ratio. Reactor temperature and space velocity are the two important process variables during
isomerization of light naphtha fraction. Reactor operating pressure and H2 /hydrocarbon ratio
do not have significant effect on the conversion of n-paraffins to isoparaffins under normal
operating conditions. Industrial isomerization units are normally operated at a molar hydrogen-to-
hydrocarbon ratio of 0.05 mol/mol at the exit of the second reactor (Graeme and van der Laan,
2003). Typical operating conditions of different isomerization processes are given in Table 2.

ISOMERIZATION CATALYSTS

Isomerization catalysts are basically dual functional in nature consisting of both metallic and
acidic functions. Metallic sites catalyze hydrogenation/dehydrogenation reactions while acidic
sites catalyze isomerization and hydrocracking reactions. Though the catalyst base possesses high
isomerization activity in the absence of metal component, it results in high initial conversion,
unstable operation, and low isomer selectivity.
Incorporation of metal component such as platinum in small amounts into the acidic base
stabilizes the conversion and lowers the initial activity. Most of the modern isomerization catalysts
contain platinum supported on different base materials. The ideal catalyst should have proper
balance between metal and acid sites, medium pore size, high dispersion of metal on surface of
catalyst, mild acidity, and strength distribution of acid sites (Newalkar et al., 2005). All commercial
isomerization processes prior to 1956 employed different catalysts such as anhydrous aluminum
chloride, silica alumina, nickel-silica-alumina, and platinum-silica-alumina as catalysts (Nelson,
1987).
Some of the recent literature deals with the hydroisomerization of model compounds (n-
hexane, n-heptane, n-decane etc.) over different bifunctional isomerization catalysts such as
Ni-Pt/SAPO 5, Ni-Pt/SAPO 11 and Pt/SAPO 41 (Eswaramoorthi and Lingappan, 2003, 2004;
Ren et al., 2006). However, industrial applications of these new catalysts are yet to be as-
certained. Aboul-Gheit et al. (1982) reported germanium as a promoter for platinum in the
presence of Cl ion during isomerization and hydrocracking of n-heptane. Aboul-Gheit et al.
586 G. VALAVARASU AND B. SAIRAM

TABLE 3
Isomerization Reaction Steps and Required Catalyst Function

Step Catalyst
No. Reaction Step Function

1 Dehydrogenation of n-paraffin to intermediate Metal

olefin
2 Carbonium ion formation from the olefin Acid
3 Rearrangement of carbonium ion to Acid
isocarbonium ion
4 Formation of iso-olefins from isocarbonium ion Acid
5 Hydrogenation of isoolefin to isoparaffin Metal

(2008) compared the isomerization activities of n-hexane using the current catalysts at different
temperatures.
Ivanov et al. (2004) studied the activity of Pt-promoted Keggin and Dawson tungstophosphoric
heteropoly acids supported on zirconia in the isomerization of n-hexane. Their studies established
the high activity of Pt/HPW/ZrO2 catalyst for n-hexane isomerization with the isohexanes yield of
80% and the selectivity of 96–98% at 190ıC. Miyaji et al. (2002) and Miyaji and Okuhara (2003)
compared selectivity and mechanism for skeletal isomerization of alkanes such as n-butane, n-
pentane, and n-heptane over zirconia-based solid acids and their Pt-promoted catalysts. They found
that the Pt-promoted solid acids were selective for isomerization in the presence of hydrogen.
The reaction steps involved during isomerization and the required catalyst function are given in
Table 3. Light naphtha isomerization process is usually categorized based on the type of catalysts
namely, chlorided alumina, zeolite, and sulfated oxide.
Chlorided alumina and zeolite-based catalysts are the two widely utilized catalysts for naph-
tha isomerization. Sulfated oxide catalysts such as sulfated zirconia-based catalysts are latest
developments in isomerization catalysis. The advantages and disadvantages of different types of
isomerization catalysts are compared in Table 4.
Though zeolite-based isomerization catalysts are very stable, easily regenerable, and tolerant
toward sulfur and water, they have certain disadvantages especially with respect to operating
temperature. Zeolite catalysts normally operate in the temperature range of 250–300ıC, which
is not thermodynamically favorable for the formation of branched isomers. The low activity of
zeolite catalysts limits the isomerate octane number to lower values in the range of 78–80 RON.
Zeolite based catalysts are very robust and operate commercially at sulfur levels exceeding 100

TABLE 4
Comparison of Isomerization Catalysts

Catalyst Advantages Disadvantages

Chlorided alumina  Offers the highest activity  Chloride addition necessary for catalyst activity
 Yields high octane isomerate  Sensitive to poisons
 Offers high isomerate yield
Zeolitic catalysts  Regenerable  Lowest activity
 Tolerant to feed poisons  Requires high temperatures and
 Very stable H2 /Hydrocarbon ratios
Sulfated-zirconia  Possess intermediate activity  Requires higher hydrogen to hydrocarbon ratio
 Tolerant to catalyst poisons
 Regenerable
 LIGHT NAPHTHA ISOMERIZATION PROCESS 587

ppm in naphtha feedstock. However, modern zeolitic catalysts are reported to possess outstanding
high isomerization activity and low selectivity to gas make (Weyda and Kohler, 2002). Zeolite-
based isomerization catalysts are regenerable and hence their active life is usually about 10 years
and more. Since zeolite based catalysts are resistant to feed poisons, extensive feed pretreatment
steps are not required and thus these catalysts offer lower capital investment.
Chlorided alumina catalysts usually operate at lower temperatures in the range of 130–170ıC
and thus do not have thermodynamic limitations on isomerization reactions. The isomerate octane
number in case of chloride alumina is 4–5 units higher compared with zeolite-based catalysts for
once-through isomerization operation. With recycle operation, chlorided alumina-based process
could achieve isomerate octane value in the range of 88–92. Since these catalysts are very sensitive
to feed contaminants such as sulfur, nitrogen, and water, removal of these impurities by specific
purification steps is required, which normally increases cost of the unit. Addition of chlorides to
maintain the catalyst activity and removal of hydrogen chloride in a caustic scrubber is required in
this process, which calls for spent caustic disposal and associated disposal problem to the refiners.
Chlorided alumina catalysts are nonregenerable and the catalyst life is usually in the range of
2–3 years. These catalysts yield more of high-octane dimethylbutanes than low-octane methyl
pentanes in once-through operation compared with zeolite-based catalysts (Ross, 2004).
Continual research efforts are in progress by different catalyst suppliers to develop alternatives
to both zeolites and chlorided alumina-based catalysts. Development of a new isomerization
catalyst, which combines the high activity of the catalyst with acceptable poison resistance, is the
goal of such research and development efforts. Some catalyst suppliers developed mixed oxide-
based isomerization catalysts with the previous objective. These mixed oxide catalysts could not
meet the process objective because they had high water sensitivity and less stable. However, some
catalyst suppliers claim to have developed a successful mixed oxide-based isomerization catalyst
with high activity and high poison tolerance.
GTC technology along with NPP Neftehim ( ) claims to have developed a leading edge
platinum-based mixed oxide catalyst for isomerization process having both low temperature
activity and high impurities tolerance (Smetters et al., 2009). Sud-Chemie ( ) claimed development
of novel metal oxide catalyst HYSOPAR-SA (SA stands for super acid) based on sulfated zirconia
combining high activity and improved tolerance towards water and sulfur (Weyda and Kohler,
2002). An improvement of about 2–3 units RON increase is reported for this zirconia-based
catalyst in comparison with zeolitic catalysts, which is closer to that obtained from chlorinated
alumina catalysts.
Isomerization catalyst activity is usually measured in terms of iso-C5 and 2,2-DMB activities.
At lower weight hourly space velocity (WHSV), most of the catalysts give similar performance
due to thermodynamic equilibrium limitations. Highly active catalysts normally give superior
performance even at higher WHSV, allowing more feed throughput or lower catalyst volume
compared with low-activity catalysts. Highly active catalysts will decrease catalyst volume and
inventory and thus reduces catalyst and platinum costs. Application of improved catalysts proves
to be a cost-effective way to de-bottleneck an isomerization unit and achieve longer life cycles
(de Boer and Johnson, 1997).

Catalyst Activation
The fresh isomerization catalyst is usually not active for carrying out the reactions. Before carrying
out isomerization reactions, the isomerization catalyst should be activated to convert it into active
form by treating with some of the chlorinating agents such as AlCl3 or CCl4 using standard
activation procedure normally provided by the catalyst supplier. Small amounts of chlorinating
agent or the activator are also added during the operation cycle to maintain the catalyst activity.
588 G. VALAVARASU AND B. SAIRAM

TABLE 5
Effect of Isomerization Catalyst Poisons and Treatment Method

Poison Effect on Isomerization Catalyst Treatment

Sulfur  Acts as a temporary catalyst poison Hydrotreating of the naphtha feed

 Inhibits catalyst activity
 Lowers conversion and octane number
 Restoration of activity by removal of sulfur
Nitrogen  Poisons acidic sites and reduces isomerization activity Hydrotreating of the naphtha feed
of the catalyst
 Causes ammonium chloride fouling of product coolers
and other downstream equipment.
Water  Irreversible poison and shortens catalyst life Molecular sieve drying of the naphtha
 Removes catalyst chlorine and reduces activity feed
 Results in equipment corrosion
Fluorides  Poison the isomerization catalyst by degrading the Passing feed over hot bed of alumina
drier molecular sieves

Catalyst Regeneration
Isomerization catalysts are prone to deactivation due to coke lay down on the catalyst surface by
hydrocracking reactions. The isomerization catalyst activity can be restored by carrying out in
situ oxidative regeneration to burn off the coke deposited on the catalyst.

Catalyst Poisons
Isomerization catalysts are very sensitive to the presence of impurities in the feedstock and
makeup gas such as sulfur, nitrogen and water. Apart from these poisons aromatics, olefins
and naphthenes also act as poisons for isomerization catalyst to a certain extent (Slade and
Zuijdendorp, 2006). The effect of various catalyst poisons on the activity of isomerization catalyst
and their treatment method is presented in Table 5. Table 6 provides the list of typical feedstock
impurities and their tolerance level on different isomerization catalysts. Proper pretreatment of the
naphtha feedstock is essential to remove these contaminants and increase the life of isomerization
catalyst.
Graeme and van der Laan (2003) studied low-density, platinum-based isomerization catalysts
(AT-10) with respect to reactor performance and catalyst activity. They concluded that these

TABLE 6
Typical Feed Impurities Tolerance of Different Isomerization Catalysts

Feedstock Chlorinated Modern Metal

Conditions Alumina Zeolite Oxide

Sulfur, ppm None < 200 < 20

Water, ppm None < 200 < 20
Aromatics/Benzene, % <2 < 10 < 2
C7C , % <2 < 5 < 2
 LIGHT NAPHTHA ISOMERIZATION PROCESS 589

catalysts could overcome maldistribution problems and improve catalyst performance measured
by PIN and isobutane ratios and characterized by higher activity, short loading, and lower costs.
They could reduce platinum content to half the levels of earlier generation C4 isomerization
catalyst for the same activity.
Selection of catalysts for a particular unit is usually based on the comparison of volumetric
activity of the catalysts. Catalyst stability is also one of the important criteria for selecting
isomerization catalyst. Normally stability is tested in pilot plant units by performing long-duration
experiments at typical operating conditions or by performing accelerated deactivation testing for
short periods. Pilot plant experiments are conducted at similar operating conditions to ascertain
catalyst initial activity in terms of isomerate PIN and octane number. The pilot plant results
cannot be directly correlated with industrial performance since there are differences between
geometry and flow regimes between pilot plant and industrial reactors. A suitable mathematical
model is necessary to correlate and scale up the pilot plant results with that of industrial unit
performance.

COMMERCIAL ISOMERIZATION CATALYST SUPPLIERS

There are several isomerization catalyst manufacturers in the market and some of them are
listed in Table 7 along with catalyst name and important features. High-activity and low-density
isomerization catalysts such as ATIS-2L developed jointly by Axens ( ) and Albamarle proved
to be effective in reducing the overall cost of catalyst for a given activity and claimed to give
a greater return on investment (Ross et al., 2004). All the AT series of catalysts are platinum
containing chlorinated alumina-based catalysts.

ISOMERIZATION REACTORS

Isomerization unit performance depends on the suitable reactor design. Due to the slow nature
of isomer forming reactions, isomerization is usually carried out in trickle bed reactors in which
the feed trickles down through the catalyst bed at a low velocity cocurrently with hydrogen
gas. Normally two reactors are used in series operation to complete isomerization reactions. In
the first reactor (lead reactor), exothermic benzene saturation reactions occur, which results in a
temperature rise of about 10–50ıC. Since high temperatures are not favorable for the isomerization

TABLE 7
List of Isomerization Catalyst Suppliers and Catalyst Features

Supplier Catalyst Name Catalyst Features

Axens ATIS–2L Low-density, low-platinum chlorinated alumina catalyst

Albamarle AT-2/AT-2G High-density platinum based C4 isomerization catalyst
AT-10 Low platinum containing C4 isomerization catalyst
AT-20 C5 /C6 isomerization catalyst with superior activity
Sud-Chemie HYSOPAR Zeolite-based catalyst
HYSOPAR SA Sulfated zirconia catalyst with high activity and improved
impurities tolerance
UOP I-82, I-84 Penex catalysts
I-122, I-124 Butamer catalysts
PI-242 Par-Isom catalyst
590 G. VALAVARASU AND B. SAIRAM

reactions due to equilibrium limitations, the effluent from the lead reactor is usually cooled and
sent to the second (lag) reactor. The second reactor is normally operated at a lower temperature
of about 110–150ıC for favorable isomer formation.

ISOMERIZATION PROCESSES BASED ON CONFIGURATION

There are two different types of isomerization processes available commercially, namely once-
through and recycle processes. In once-through isomerization, there is no recycle of the reactor
product resulting in lower isomerate octane number (78–84) compared with recycle processes.
Recycle isomerization units achieve higher octane number (88–92) in isomerate due to recycle
of low-octane unconverted n-paraffins (n-pentane and/or n-hexane) again into the reactor after
separation from the reactor product. The most common recycle scheme introduces a deisohexanizer
to recycle n-C6 and lower octane methylpentanes to the isomerization reactor. For attaining higher
octane numbers, complete recycle of all normal paraffins to the reactor is required rather than
adopting once-through or partial recycle options (Ross, 2004). Separation and recovery of the
unconverted normal paraffins from their isomers play a major role in isomerate octane quality.
The separation of the normal paraffins from isoparaffins can also be accomplished by vapor phase
adsorption of the n-paraffins on a molecular sieve bed, which uses the difference in sizes of the
various molecular components for separation.

COMMERCIAL ISOMERIZATION PROCESSES

There are various commercial processes available for isomerization of butane and light naphtha.
Some of these commercial processes are briefly described in the following sections.

UOP Isomerization Processes

UOP is a dominant player in the field of isomerization technology with Penex (C5/C6) and
Butamer (C4) processes. UOP also has other isomerization processes such as Par-Isom and total
isomerization process TIP. In fact, the first hydroisomerization unit was built by UOP in 1953.

Butamer Process
UOP Butamer process was commercialized in 1959 using dual functional isomerization catalyst.
This process is used for the isomerization of n-butane to isobutene, which will further be utilized
in other processes.

Penex Process
UOP Penex process is specifically designed for the catalytic isomerization of light straight run
naphtha stream containing pentanes, hexanes, and mixtures of them to improve the octane number.

Par-Isom Process
UOP Par-Isom is a light naphtha isomerization process using a nonchlorided alumina catalyst.
The catalyst used in this process is regenerable and water tolerant. The existing idle reformers or
hydrotreaters can be converted to the Par-Isom process.
 LIGHT NAPHTHA ISOMERIZATION PROCESS 591

Axens Isomerization Processes

Axens provides a range of isomerization processes based on conventional as well as advanced
technologies. The conventional technologies include once-through and deisohexanizer recycle
designs and the advanced technologies include Ipsorb and Hexorb processes. The conventional
once-through design utilizes chlorinated alumina catalyst with two reactors in series. The Ipsorb
unit is claimed to yield an isomerate with an octane number of 89 compared with the conventional
deisohexanizer (DIH) recycle route, which gives an octane number of 88.

Axens Ipsorb Isomerization Process

In Ipsorb process fresh feed is initially sent to a deisopentanizer column, the bottom of which
feeds the isomerization reactor loaded with chlorinated alumina catalyst. The isomerate after
stabilization goes for molecular sieve section to separate and recycle all unconverted n-paraffins by
adsorption/desorption cycles. The de-isopentanizer removes most of the isopentanes from reactor
charge and also reduces the fresh feed dehydration requirements due to its ability to dehydrate
raw feed by distillation (Ross, 2004).

Axens Hexorb Isomerization Process

Hexorb process uses isohexane to desorb normal paraffins from the molecular sieves by
pressure swing technique. This process yields higher isomerate octane (2–3 units) and addresses
methylpentane issue more fully compared to Ipsorb process.

BP Isomerization Process
This process is licensed by British Petroleum Company (BP) utilizing a flexible Pt-alumina catalyst
treated with CCl4 for the upgradation of C5 /C6 or C4 fractions in single pass operation. Greenough
and Rolfe (1986) discussed various aspects of BP isomerization process with respect to process
description, product yields and process economics.

Shell Hysomer Process

Shell Hysomer process is based on metal-loaded molecular sieve zeolite catalyst with high
tolerance for impurities such as sulfur and water. This process claims to achieve an octane
improvement of 10–12 units in light naphtha fractions (Cusher, 1986a).

TIP With IsoSiv Adsorption

TIP is a shell technology, which integrates both Hysomer unit with Isosiv adsorption technology
(Cusher, 1986b). This process claims to increase the octane number of the feed naphtha by 20
units by total isomerization of all n-paraffins present in the feed.

GTC Isomerization Technology

GTC Technology along with Niftehim claims to have an isomerization technology with platinum-
based mixed oxide catalyst system. They offer four different isomerization process schemes with
once through and recycle schemes.
Many new processes appear in the area of hydroisomerization of naphtha especially to improve
the octane number. Ducreux and Jolimaitre (2004) invented a process for producing high-octane
number gasoline using a process combining hydroisomerization and adsorptive separation using
a microporous solid zeolite adsorbent.
592 G. VALAVARASU AND B. SAIRAM

TABLE 8
Important Catalyst Features and its Advantages

Catalyst Feature Advantage

High water tolerance Eliminates the need for feed and hydrogen dryers
High sulfur tolerance Eliminates or reduces HDS costs
Regenerability Reduces catalyst replacement cost
Elimination of addition of Results in lower construction material cost and
chlorides eliminates facilities for effluent treatment system

ISOMERIZATION PROCESS AND CATALYST FEATURES

In the selection of suitable isomerization process, oil refiners seek for the important process
features such as catalyst activity and poison resistance, catalyst life, capital investment, and
operating cost. Some of the important catalyst features and its advantages are presented in Table 8.

CATALYTIC REFORMING VERSUS ISOMERIZATION PROCESSES

Both catalytic reforming and isomerization are basically upgrading processes for refinery naphtha
streams to improve the octane number of the naphtha. However, these processes have many
differences between them, especially with respect to feedstock, operating parameters, and product
quality. Catalytic reforming process is basically used to upgrade heavy naphtha stream (C7C ) while
isomerization process upgrades light naphtha streams in the range of C5 /C6 . Reforming mainly
produces high-octane aromatics from low-octane paraffins and naphthenes while isomerization
converts low-octane n-paraffins into high-octane isoparaffins, which are the desired hydrocarbons
in gasoline. The comparison of process conditions of catalytic reforming and isomerization is
presented in Table 9.

ISOMERIZATION FOR BENZENE REDUCTION

Benzene content in gasoline is being limited to 1.0 vol% in most of the countries. U.S. Mobile
Source Air Toxics (MSAT) II regulations further reduce benzene to less than 0.62% in all U.S.
gasoline by 2011 (Almering et al., 2008). Isomerization is one of the options to reduce benzene

TABLE 9
Comparison of Catalytic Reforming and Isomerization
Process Conditions

Catalytic
Parameters Reforming Isomerization

Reactor temperature, ı C 490–520 120–260

Operating pressure, kg/cm2 5–20 15–35
WHSV, hr 1 1–5 1–3
H2 /HC ratio, mol/mol 5–10 1–4
 LIGHT NAPHTHA ISOMERIZATION PROCESS 593

from gasoline pool. Isomerization process can also be coupled with benzene saturation process to
partially regain the loss in octane number due to saturation of benzene in the reformate stream
(Smetters et al., 2009).
The combination of catalytic reforming and isomerization allows refiners to process various
feedstocks such as straight run and cracked naphtha streams while adding more octane barrels into
the gasoline pool. Patents by Schmidt and Raghuraman (1992) and Franck et al. (1990) deal with
the combination of isomerization and catalytic reforming for producing reformulated gasoline.
Prefractionation of reformer feed to separate low-octane C5 and C6 components and subsequent
isomerization of this benzene rich stream will result in both octane improvement of about 20–
22 units and benzene reduction. The resulting octane-barrel increase in the gasoline pool give
the refiner much greater flexibility in balancing reforming severity for cycle-length improvement,
reformate yield increase, benzene reduction or increase in hydrogen production (Ross, 2004). Low
et al. (1991) discussed reduction of benzene in gasoline pool by a process that hydrogenates a
benzene containing isomerization feedstream. Fersing and Nascimento (2002) discussed a catalytic
process for the isomerization of a hydrocarbon charge containing a substantial quantity of paraffin
hydrocarbons with 5 or 6 carbon atoms and a benzene content that is greater than or equal to 2%
by weight.
In conventional processing, benzene saturation occurs in a separate reactor prior to isomeriza-
tion to limit benzene content to isomerization unit, which will increase capital cost. Combined
processing of light reformate and light straight run naphtha in a catalytic distillation (CD)
hydrocolumn followed by C5 /C6 isomerization will result in complete benzene saturation with
respect to MSAT II requirements as well as octane improvement in a cost-effective manner
(Almering et al., 2008).

MODELING AND SIMULATION OF ISOMERIZATION PROCESS

Most of the reactions occurring during isomerization are similar to catalytic reforming reactions
such as isomerization of n-paraffins and naphthenes, saturation of aromatics, and hydrocracking of
straight-chain hydrocarbons. Also isomerization reactions are carried out in trickle bed reactor over
Pt/Al2 O3 catalysts similar to catalytic reforming. On the feedstock level, isomerization has similar-
ities with catalytic reforming since these feeds can easily be characterized for detailed hydrocarbon
analysis. Thus modeling and simulation of isomerization process has many similarities with that
of catalytic reforming process and models for later process is available in literature (Bommanan
et al., 1989; Padmavathi and Chaudhuri, 1997; Taskar and Riggs, 1997). Isomerization process
can be modeled using lumped kinetic approach with the feed being lumped into many different
hydrocarbon species. Various reactions can be written for these lumps and kinetic parameters
obtained from pilot plant experiments.

FUTURE AREA OF WORK

Since isomerization is gaining importance, continuous research efforts are being undertaken by
catalyst suppliers and process licensors with respect to the following:

 Development of improved catalysts with high activity and impurities tolerance

 Reactor developments to minimize maldistribution and increase catalyst wetting
 Improved catalysts with high benzene saturation activity for minimizing benzene content in
isomerate and processing high benzene feedstock
594 G. VALAVARASU AND B. SAIRAM

CONCLUSIONS

The isomerization process was reviewed with emphasis on reaction chemistry, catalyst develop-
ments, recent advances in process technology, and commercial processes. Various isomerization
processes based on different catalysts were compared in detail with their advantages and disad-
vantages. This review will be useful to refiners for the selection of suitable technology for their
isomerization units to upgrade their naphtha streams with respect to octane number and benzene.

ACKNOWLEDGMENTS

The authors thank the management of Chennai Petroleum Corporation Limited for allowing to
publish this paper.

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