Isomerization in Petroleum Processing

Dana Sullivan, Stephen Metro, and Peter R. Pujadó

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 480
History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481
Market Trends and Regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
Market Trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
Regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484
Process Chemistry of Paraffin Isomerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
Primary Reaction Pathways . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 486
Isomerization Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
Chlorided Alumina-Type Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 489
Zeolitic-Type Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 489
Sulfated Metal Oxide-Type Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 490
Process Options . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 490
Isomerization Process Flow Schemes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 491
Isomerization Process Economics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 494
Catalyst Suppliers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 495
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 495
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 496
Further Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497

Abstract
Upgrading light hydrocarbon (C4–C7) streams in refineries, petrochemical
plants, and gas processing plants has continued to increase in commercial
application, as the world demand for gasoline and petrochemicals has

Peter R. Pujadó has retired.

D. Sullivan • S. Metro (*)
UOP LLC, A Honeywell Company, Des Plaines, IL, USA
e-mail: dana.sullivan@honeywell.com; stephen.metro@honeywell.com
P.R. Pujadó
UOP LLC, A Honeywell Company, Kildeer, IL, USA

# Springer International Publishing Switzerland 2015 479

S.A. Treese et al. (eds.), Handbook of Petroleum Processing,
DOI 10.1007/978-3-319-14529-7_7
480 D. Sullivan et al.

experienced steady growth over the past decade. Increasingly stringent regula-
tions have been enacted in most regions of the world, driving the increased
demand for clean fuels. As a result, gasoline composition has been adjusted to a
greater extent using C5–C7 isomerization processes. Light-naphtha isomeriza-
tion technology plays a key role in meeting octane demand in the gasoline pool
for clean fuels and premium gasoline grades. Low octane naphtha feedstocks
are processed into isomerate with an octane number ranging from 80 to
93 RON. Isomerization involves the skeletal isomerization of a paraffin to a
more highly branched paraffin with the same carbon number. Several light
paraffin isomerization technologies are reviewed in this chapter, including
both process and catalyst technologies. Flow schemes and economics are
reviewed. Catalyst technologies include Pt containing zeolitic, mixed-metal
oxide, and chlorided alumina.

Keywords
Paraffins • Isomerization • Gasoline • Light naphtha • Butane • Pentane •
Hexane • Octane number • Chlorided alumina • Sulfated metal oxide • Zeolite

Introduction

Upgrading light hydrocarbon (C4–C7) streams in refineries, petrochemical plants,

and gas processing plants has continued to increase in commercial application, as
the world demand for gasoline and petrochemicals has experienced steady growth
over the past decade. Increasingly stringent regulations have been enacted in most
regions of the world, driving the increased demand for clean fuels. As a result,
gasoline composition has been adjusted to a greater extent using C5–C6 isomeriza-
tion processes. These regulations include many clean fuel initiatives, including lead
phaseout, minimization of benzene, aromatics and olefin content, and addition of
oxygenates to gasoline.
Light-naphtha isomerization plays a key role in meeting octane demand in
the gasoline pool for clean fuels and premium gasoline grades. Low-octane
naphtha feedstocks are processed into isomerate with an octane number ranging
from 80 to 93 RON, depending on the process configuration, catalyst type, and
operating conditions. Isomerization involves the skeletal isomerization of a
paraffin to a more highly branched paraffin with the same carbon number.
As in alkylation, which is discussed elsewhere in this handbook, the more highly
branched paraffins have higher octane numbers. However, because of its nature,
isomerization may also affect some of the naphthene components and will also
saturate aromatics. Based on its chemistry, the isomerization process is one of the
most economic means available for reducing the benzene content in gasoline.
Several isomerization technologies are commercially available from various
licensors. These are fixed-bed process units that employ high-activity catalysts.
The reaction conditions promote isomerization and minimize hydrocracking.
The first commercial isomerization process dates back to the 1930s for
Isomerization in Petroleum Processing 481

isomerization of normal butane to isobutane. Isomerization of C5–C6 paraffins for

motor fuel blending was introduced in the late 1950s.
UOP developed the Butamer™ process for the isomerization of n-butane to
isobutane, typically used as a feedstock to produce motor fuel alkylate. Isobutane
produced from isomerization can also be converted to isobutylene via catalytic
dehydrogenation using a process such as the UOP Oleflex™ process. Isobutylene is
used to produce gasoline blending components such as MTBE and ETBE and for
making petrochemicals such as butyl rubber.
The aforementioned processes are some of the most widely used in industry and
form the basis of this discussion. Developments in light-naphtha isomerization are
usually based on the introduction of new, more active or more stable catalysts, some
of which will be discussed in more detail below.
The skeletal isomerization of paraffins is one of the many important industrial
applications of acid function-promoted catalysis. Other examples of the wide
commercial applications of acid-catalyzed industrial hydrocarbon reactions are
the alkylation of paraffins and aromatics with olefins, transalkylation and dispro-
portionation of aromatics, metathesis of olefins, oligomerization of olefins,
etherification and hydration of olefins, and hydrocracking. Although these various
applications have some similarities, they are all promoted by an acidic catalyst and
often by a metal function. The specific catalytic requirements for achieving a
favorable economic result have led to the proliferation of specialized catalytic
materials.

History

In the 1930s, Vladimir Ipatieff and his team from UOP discovered that they could
transform normal butane molecules in gasoline to isobutane using an aluminum
chloride catalyst with hydrogen chloride as a cocatalyst (Remsberg and Higdon
1994). While scientifically interesting at the time, refiners did not want isobutane in
their gasoline due to its high volatility. But before the decade was over, high-octane
aviation fuel was being produced from alkylation and isomerization processes and
became a significant factor in the war effort during World War II. The UOP
Butamer™ process was the predominant process used for n-butane isomerization
then, as it is today. HF alkylation was subsequently used to produce higher-octane
motor fuel for automobiles by combining isobutane with isobutylene to form highly
branched isooctane molecules with eight carbon atoms. This gasoline had a high
octane number and burned cleanly in combustion engines.
Demand for high-octane fuels for automotive use continued to increase in the
late 1950s and 1960s as part of postwar economic expansion. It was recognized that
the light straight-run naphtha portion of crude oil, consisting of predominantly
pentanes and hexanes, negatively affects gasoline quality. A catalyst similar to what
was used in the Butamer process was applied by UOP scientists to pentane- and
hexane-rich naphtha and found to increase octane by 12–20 numbers. This UOP
process, named the Penex™ process, was soon being used in nearly all refineries.
482 D. Sullivan et al.

Fig. 1 Isomerization process configurations and octane values

Over the last half century, there has been an evolution in both the flow scheme
and catalysts used in light-naphtha isomerization processes. Flow scheme improve-
ments include the use of a recycle loop to circulate unreacted hydrocarbons exiting
the reactor back to the reactor inlet and the use of fractionators such as a deisopen-
tanizers (DIP) and deisohexanizers (DIH), and a process section that separates iso-
and normal paraffins via a molecular sieve, rerouting the normal paraffins back to
the reaction section for further yield improvements.
Catalyst advances include the use of new materials and base formulations to increase
activity, selectivity, and the life of chlorided alumina-type catalysts. Other catalyst
technologies were developed that did not require the continuous use of a chloriding
agent during production to maintain catalyst activity and catalysts that were regenerable.
Regenerable catalysts include older-generation zeolitic types, as well as more recent
mixed metal oxide types (zirconia). A discussion on these types of catalysts and process
technologies follows in latter sections, which are depicted in Fig. 1. A number of
technology companies introduced various isomerization catalysts over the years, includ-
ing Akzo Nobel NV (now Albemarle), Axens, NPP Neftekhim, S€ud-Chemie AG (now
Clariant), Shell Chemicals LP, and UOP (Honeywell UOP LLC).

Market Trends and Regulations

Market Trends

The gasoline available to consumers consists of a mixture of gasoline fractions from

many refinery sources, including straight-run naphtha (unprocessed fraction),
isomerate, alkylate, reformate, polymer, and FCC fractions. Gasoline also contains
Isomerization in Petroleum Processing 483

Gasoline Consumption by Region, 2000 – 2013

25000

20000 China
OAP
India
BPDx1000

15000
Middle East
Africa
10000 CIS Region
Latin America

5000 Europe
North America

0
2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013

Fig. 2 Overall gasoline demand by region

additives such as ethanol, used to lower emissions via oxygenate addition, boost
octane, and consume a “biofuel” source, which is typically produced from corn and
sugarcane. Gasoline demand has risen from
20 M B/D in 2000 to 23 M B/D in
2013 (IHS CERA 2014) as per Fig. 2. Gasoline demand is expected to rise to 28 M
B/D over the next decade as per multiple market forecasting resources.
About half of the current demand is in developed regions such as North America,
Europe, and Japan (IHS CERA 2014). Growth has been categorized as flat to declining
in these regions due to the increased use of ethanol in gasoline, increased use of diesel,
improved automobile fuel efficiencies, changing demographics, etc. The strongest
growth over the past decade has occurred in emerging regions such as Asia, Latin
America, the Middle East, and Russia, which currently make up approximately 50 %
of gasoline demand (IHS CERA 2014), expected to rise by an additional 10 % over the
next decade. The drivers for growth include large, growing populations and econo-
mies, increased wealth, and export of goods and services. These in turn are driving
increased demand for automobiles and roadways and ultimately transportation fuels.
Isomerate makes up approximately 5 % of the total gasoline pool worldwide,
highly dependent upon geographical region, typically being driven by meeting local
gasoline specifications and demand. The global isomerization capacity is approx-
imately 2.5 million barrels/day (IHS CERA 2014). While the largest installed
capacity is in North America and Europe, almost 60 %, rapid growth is occurring
in Russia, the Middle East, and Asia. The overall growth of isomerate over the past
decade has been approximately 5 %, more than double gasoline growth, due to the
increase in focus on clean fuels.
Some of the “developed” regions such as the USA and Europe, which
are “octane long,” have been operating their isomerization units to primarily
saturate benzene to meet gasoline benzene requirements. Some allow their isom-
erization catalyst to deactivate from untreated feed poisoning, but still function to
saturate benzene, using only the catalyst’s metal function.
484 D. Sullivan et al.

Table 1 Euro fuel specifications

EN DIR DIR DIR DIR
Directive 228 98/70 98/70 98/70 98/70
Euro fuel Year 1993 1996 2000 2005 2009
specifications Class Euro 1 Euro 2 Euro 3 Euro 4 Euro 5
Aromatics Vol Max No No limit 42 35 35
% limit
Olefins Vol Max No No limit 18 18 18
% limit
Benzene Vol Max 5 5 1 1 1
%
Oxygen Wt Max 2.5 2.5 2.7 2.7 3.7
%
Sulfur ppm Max 1,000 500 150 50 10
RON Min 91 92 93 94 95
RVP kPa 35–100 35–100 60–70 60–70 60–70
Lead g/lt Max 0.013 0.013 None None None

Regulations

Gasoline is subject to many local, national, and international regulations. New

regulations affecting gasoline composition have been enacted in most regions of
the world, driving the increase in demand for clean fuels. These regulations include
many clean fuel initiatives, such as lead phaseout, minimization of RVP, limits on
sulfur, benzene, aromatics, and olefin content, and addition of oxygenates. For
example, Euro 5 motor fuel specifications, last updated in 2009, limit aromatics to
35 vol.%, olefins to 18 vol.%, and benzene to 1 vol.% maximum. Half a decade
later, many non-EU countries are still in the planning phases of implementing either
Euro IV or Euro V specifications. Refer to Table 1 for Euro I–V gasoline specifi-
cations (Euro Fuel Specifications).
In the USA, the Environmental Protection Agency (EPA) sets the fuel stan-
dards, with some variations from state to state, and California is generally being
most stringent. Gasoline specifications are set by CARB, or the California Air
Resources Board, and have the following fuel specifications that are similar to
Euro V: 35 vol.% aromatics, maximum; 1.1 vol.% benzene, max; 10 vol.% olefins,
max; 10 vol.% ethanol, min; RVP 6.4–7.2 psi; and sulfur <20 wt ppm. It should
also be noted that the US EPA’s Tier 3 sulfur limits have been set to 10 wt ppm
maximum by 2017.
As indicated above, benzene content in gasoline is one component broadly
regulated. For instance, in the USA, the Environmental Protection Agency (EPA)
has implemented a Mobile Source Air Toxics (MSAT) rule to reduce hazardous air
pollutants (US EPA 2014). As of 2011, the EPA requires that refiners must
meet a maximum annual average gasoline benzene content of 0.62 vol.%.
The maximum permissible level is 1.3 vol.% as of July 2012. These are applied
to US refiners, as well as to gasoline imported to the USA. There are numerous
Isomerization in Petroleum Processing 485

technologies available to address lowering benzene content including

prefractionation, saturation, isomerization, and extraction, and they are a subject
of other literature (Shecterle 2008).
The C5–C6 isomerization unit is typically part of a naphtha complex used to
produce gasoline. The naphtha feed is typically hydrotreated to remove contami-
nants harmful to downstream processes. The naphtha feed is divided into lighter
and heavier fractions using a naphtha splitter. The lighter fraction, typically
a C5–C6 hydrocarbon fraction, is sent to the isomerization unit, whereas the heavier
fraction, typically C7+ hydrocarbons, is sent to the catalytic reforming unit. The
reforming unit converts these naphthas rich in paraffins and naphthenes to a product
that is high in octane number and rich in aromatic hydrocarbons, using a platinum-
containing acidic catalyst at elevated temperatures and pressures.

Process Chemistry of Paraffin Isomerization

The octane rating of the components used in the manufacture of the various
commercial gasoline grades is indicative of the antiknock quality of a given fuel
or component. The inherent octane values of different hydrocarbons have led to a
variety of processing strategies to produce high-octane components for the pro-
duction of high-performance motor fuel. In the case of C5 and C6 paraffins, the
most highly branched isomers have the highest octane values. In the case of
butanes, octane is somewhat irrelevant because the majority of isobutane is
consumed in the production of motor fuel alkylate. Octane values for C5 and C6
paraffin isomers are shown in Table 2. The two empirical octane measurement
methods for research (ASTM Method 2699) and motor (ASTM Method 2700)
measure antiknock characteristics at two severity levels. Often, the average of
these two values, or (R + M)/2, is used to express the overall engine performance of
a gasoline component or blend. Table 2 shows that isopentane has a Research
Octane Number (RON) value of nearly 30 numbers higher than n-pentane (Phys-
ical Constants of Hydrocarbons C3-C10 1971).

Table 2 Hydrocarbon octane values

Research octane by ASTM Motor octane by
2699 ASTM 2700 (R + M)/2
n-Butane 93.8 89.6 91.7
i-Butane 100.4 97.6 99.0
n-Pentane 61.7 62.6 62.2
i-Pentane 92.3 90.3 91.3
n-Hexane 24.8 26.0 25.4
2-Methylpentane 73.4 73.5 73.4
3-Methylpentane 74.5 74.3 74.4
2,2-Dimethylbutane 91.8 93.4 92.6
2,3-Dimethylbutane 101.0 94.3 97.6
486 D. Sullivan et al.

Fig. 3 Butane equilibrium 100

80
Butane
60 Normal

mole %
Isobutan
e
40

20

0
40 150 260 370 480
Temperature, °C

100

80
Isopentane
60
mole %

40
Pantane
Normal
20 Neopentane

0
40 150 260 370 480
Fig. 4 Pentane equilibrium Temperature, °C

Similarly, the multibranched hexane isomer 2,2-dimethylbutane (2,2-DMB) has

a RON about 67 numbers higher than n-hexane. The single-branched isomer
2-methylpentane (2-MP) has a RON only about 49 numbers higher than n-hexane.
Clearly branched isoparaffins and in particular multibranched isomers are the
desired components for gasoline production.
Thermodynamic equilibria for the branched paraffin isomers are generally
favored by low temperatures. Figures 3, 4, and 5 illustrate this trend (Stull
et al. 1987). The most active catalyst, when all other variables are equal, is capable
of producing the highest octane products.

Primary Reaction Pathways

Paraffin isomerization is most effectively catalyzed by a dual-function catalyst

containing a noble metal and an acid function. The reaction is believed to proceed
through an olefin intermediate, which is formed by paraffin dehydrogenation on the
metal site (Reaction (1)):

Pt
(1)
CH3CH2CH2CH3 ! CH3CH2CH ¼ CH2 þ H2 :
Isomerization in Petroleum Processing 487

Fig. 5 C6 fraction 100

equilibrium
80 CH)
/ (M CP+
MCP

mole %
60
2−MP + 3−MP / ΣC6 Paraffins
40 2, 2−DMB /
ΣC Paraffins
6

/ ΣC Pa ra ffi ns
20 n−Hexa ne 6
2, 3−DMB/ΣC6 Paraffins

0
93 149 204 260 316
Temperature, °C

Although the equilibrium conversion of the paraffin in Reaction (1) is low at

paraffin isomerization conditions, sufficient olefins are present to be converted to
a carbonium ion by the strong Brønsted acid site (Reaction 2):

þ
(2)
CH3CH2CH ¼ CH2 þ ½Hþ ½A  ! CH3CH2CHCH3 þ A :

The formation of the carbonium ion removes product olefins from Reaction (1) and
allows the equilibrium in Reaction (1) to proceed. The carbonium ion in Reaction
(2) undergoes a skeletal isomerization, possibly through a cycloalkyl intermediate
as shown in Reaction (3).

CH2CH3
+ +
CH3−CH2−CH−CH3 → CH2 C−CH3 → CH3−C−CH3. ð3Þ
+
cyclopropyl
cation

Reaction (3) proceeds with difficulty because it requires the formation of a primary
carbonium ion at some point in the reaction. Nevertheless, the strong acidity of
isomerization catalysts provides enough driving force for the reaction to proceed at
high rates. The mechanism of the final step is disputed. The isoparaffinic carbonium
ion may be converted to an olefin through loss of a proton to the catalyst site and
then quickly be hydrogenated to the analogous isoparaffin (Reactions 4A and 4B),
or it may form the isoparaffin by hydride transfer from a normal paraffin, forming
a normal carbonium ion intermediate as well as an isoparaffin (Santen 2012)
(Reaction 5):

CH3 CH3
ð4AÞ
CH3−C−CH3 + A− → CH3−C=CH2 + [H+] [A−]
+
488 D. Sullivan et al.

CH3 CH3
pt ð4BÞ
CH3−C = CH2 + H2 → CH3−CH−CH3.

Or

CH3 CH3

CH3−C−CH3 + CH3−CH2−CH2−CH3 → CH3−CH−CH3 + CH3−CH2−CH−CH3

+ +
ð5Þ

In addition to these primary reaction pathways, there is evidence indicating the

existence of a bimolecular reaction mechanism, particularly for butane isomeriza-
tion. The olefinic intermediates dimerize, internal carbon atoms are protonated,
skeletal isomerization occurs, and the dimer undergoes beta scission that results in
the product isoparaffin. In addition to the C13 labeling experiments that support this
mechanism, a relatively small amount of hydrocarbons containing carbon numbers
higher than the feed are always found in the reaction products.

Isomerization Catalysts

Operation at the lowest temperature results in the formation of the highest octane
product (Table 2 and Figs. 3, 4, and 5) in this equilibrium-limited reaction. Having the
highest catalyst activity and the lowest operating temperature is important to achieve an
economic operation. In the previous discussion of the primary reaction pathway, the
primary functionality of a paraffin isomerization catalyst is to protonate a secondary
carbon atom. All known paraffin isomerization catalysts have a combination of strong
Lewis and Brønsted acid sites, which result in varying levels of protonation activity.
In addition to a strong acid function, isomerization catalysts must also be
capable of hydrogenolysis, which not only assists in the protonation step but also
serves to saturate olefin intermediates and aromatic hydrocarbons and to assist in
the ring opening of naphthenes. This function also gives activity stability to
isomerization catalysts, thereby improving the process economics.
An aluminum chloride catalyst for alkane isomerization was first developed in
the 1930s (Pines 1981). The original application was for the conversion of n-butane
to isobutane, which was, and still is, reacted with C3, C4, and C5 olefins to produce
motor fuel alkylate. The first application of this high-octane product was in the
production of high-octane aviation gasoline. Subsequent developments of this
predominantly Lewis-acid catalyst resulted in the current alumina-supported,
bifunctional catalyst. UOP’s I-8 catalyst is one commercial example of this catalyst
system, which has seen wide commercial applications since 1981. The current
state-of-the-art isomerization catalysts are UOP I-82 and I-84 catalysts and
Isomerization in Petroleum Processing 489

Albemarle’s ATIS-2L, introduced in the 2000s, providing higher activity and

conversion for C5/C6 applications.

Chlorided Alumina-Type Catalysts

Chlorided alumina, the highest-activity paraffin isomerization catalyst available,

increases the octane of a typical light-naphtha stream from about 70 to as high as
86 RON in a once-through paraffin isomerization unit as depicted in Fig. 1. Higher
product octane, up to 93 RON, can be obtained by recycling low-octane hydrocarbons
back to the reactors for further upgrade. The C5+ yield from chlorided alumina catalysts
is generally the highest from any commercial catalyst because of high catalyst selec-
tivity and low operating temperature. Because chlorided alumina systems are not
economically regenerable either within the process unit or ex situ, eventual reloading
may be required, depending upon contaminant levels contained in the feed and process
gas streams. While the average life of a catalyst load is 5 years, there are catalyst loads
operating well beyond 20 years with diligent care and operations monitoring.
Nevertheless, the chlorided alumina system is often the most economical choice
because of its inherent high activity. In addition, only chlorided alumina catalysts
have enough activity to economically and effectively isomerize butanes. Approx-
imately 85 % of the installed isomerization processes today employ chlorided
alumina-type catalysts.

Zeolitic-Type Catalysts

Zeolitic isomerization catalysts, such as UOP’s HS-10 Hysomer™ catalyst, operate

at higher temperatures than chlorided alumina catalysts. Almost no new process
units employ this technology due to unfavorable economics. The maximum product
octane that can be achieved is limited by the unfavorable equilibrium at these
conditions. Yields are also lower as a result of the higher operating temperature
and the less selective characteristics of zeolitic catalysts. A typical octane upgrade
for a once-through zeolitic isomerization unit is from 70 to about 79 RON. Higher
product octanes (86–88) can be obtained in a recycle operation, such as in a UOP
TIP™ unit (Total Isomerization Process) as depicted in Fig. 1. A TIP unit uses a
multi-vessel vapor-phase adsorption process (IsoSiv™ process) to separate normal
paraffins so they can be recycled to the reactor.
The most attractive benefit of zeolitic isomerization catalysts is that they are not
permanently deactivated by water or other oxygenates and are fully regenerable.
Consequently, zeolitic catalysts have often been used when revamping other pro-
cess units, such as hydrotreaters or reformers to isomerization service. Sulfur can be
present in the feedstock with catalysts such as the HS-10 catalyst, but performance
is debited to some extent. Sulfur suppresses the platinum function as it does in any
platinum-containing catalyst. Although isomerization activity is maintained, a net
C5+ product yield loss results. Feed hydrotreating is not an absolute requirement
490 D. Sullivan et al.

with zeolitic catalysts, but it is necessary to get the optimum performance from the
catalyst. Approximately 30 zeolitic-type units still operate today.

Sulfated Metal Oxide-Type Catalysts

Sulfated metal oxide catalysts, which have been described as solid superacids,
exhibit high activity for paraffin isomerization reaction (Gosling et al. 1998)
when compared to zeolitic-type catalysts. These metal oxides form the basis of a
more recent generation of isomerization catalysts that have been actively discussed
in the scientific literature. These catalysts are most commonly tin oxide (SnO2),
zirconium oxide (ZrO2), titanium oxide (TiO2), tungstated zirconia, or ferric oxide
(Fe2O3) that has been sulfated by reaction with sulfuric acid or ammonium sulfate.
Sulfated alumina is not an active catalyst for hydrocarbon reactions.
A typical metal oxide catalyst, such as UOP’s PI-244 Par-Isom™ catalyst, has a
considerably higher activity than that of traditional zeolitic-type catalysts, and this
activity advantage is equivalent to about 80  C lower reaction temperature. The
lower reaction temperature allows for a product with a significantly higher product
octane, about 82 RON for a typical feed, four numbers higher than that of a zeolitic
catalyst. Similar to zeolitic catalysts, the PI-244 catalyst is not permanently
deactivated by water or oxygenates in the feedstock. These catalysts are also fully
regenerable using a simple oxidation procedure that is comparable to the one used
for zeolitic catalysts. The high activity of the PI-244 catalyst makes it an ideal choice
for new units where the full performance advantage of chlorided alumina catalysts is
not required or where the refiner is concerned about contaminants in the feedstock.
The performance of well-established commercial isomerization catalysts such as
UOP HS-10 (zeolitic), UOP LPI-100 (an older-generation sulfated zirconia catalyst),
UOP PI-244 (modified sulfated zirconia), and UOP I-82 (chlorided alumina) catalysts
is compared in Fig. 6, which illustrates the octane number improvement over zeolitic
catalysts for all the catalysts as a function of average reactor bed temperature. This
ranking illustrates the activity advantage for the chlorided alumina-type catalyst over
the zeolitic-type catalysts, an advantage that translates directly to octane improvement.
This is particularly true for fixed volume systems, when considering reloading existing
process units. Likewise, this ranking shows the performance benefit of the first- and
second-generation sulfated zirconia-type catalysts over zeolitic. It should be noted that
for unconstrained new unit designs, additional catalyst volume can be added to attain
lower temperature operation and higher octane. Comparisons of chlorided alumina
(I-82) and sulfated zirconia (PI-244) catalysts are provided in the following sections.

Process Options

Two process options are commercially available via either chlorided alumina-type
catalyst (e.g., the Penex process with I-82) or sulfated zirconia catalyst (e.g., the
Par-Isom process with PI-244). Both provide excellent upgrading of light naphtha
Isomerization in Petroleum Processing 491

Fig. 6 Octane/activity curves for various isomerization catalyst types

with respect to octane number, yield, and octane barrels. A full techno-economic
assessment is required for final process selection, with one simple example
presented below as a case study.
Penex process units with chlorided alumina-type catalysts are most prevalent,
historically provided the highest activity, yield, and RON. While they can employ a
once-through (OT) configuration and avoid the need for an expensive recycle gas
compressor and loop, it requires continuous chloride addition to maintain isomer-
ization acid activity, requiring the use of a caustic scrubber to neutralize HCL in the
off-gas and to eliminate unit corrosion (Fig. 7). Operating costs include chloride,
caustic, and spent caustic disposal. In addition, these systems also require feed and
make-up gas driers for moisture removal to ensure long catalyst life.
The sulfated zirconia-type units do not require the chloride or caustic, the
catalyst is regenerable, but do require the use of a recycle gas compressor loop.
There are benefits and trade-offs for both systems which are summarized
in Table 3.

Isomerization Process Flow Schemes

The introduction of recent catalyst systems, such as the PI-244 catalyst, allows the
development of new process technologies that fully utilize the characteristics of
the catalyst. The process technology developed for the PI-244 catalyst is the
Par-Isom™ process. A simplified flow scheme for the Par-Isom process operating
in a once-through hydrocarbon configuration is shown in Fig. 8. For simplicity, a
once-through hydrocarbon flow scheme is discussed in this chapter. Recycle
492 D. Sullivan et al.

Fig. 7 Penex unit process flow scheme, hydrogen once-through (HOT)

Table 3 Comparison of process requirements for various catalyst types

Chlorided alumina Sulfated zirconia Zeolitic
Chemical injection Chloride None None
Contaminant sensitivity Yes No No
Equipment Dryers + scrubber Basic Fired heater
Spent caustic stream Yes No No
Heating medium MP steam MP steam Fired heater
Metallurgy CS CS Alloy
Recycle compressor No Yes Yes

hydrocarbon flow schemes previously developed for naphtha isomerization use

either molecular sieve separation, such as in a TIP unit, or fractionation, such as a
deisohexanizer (DIH) column.
The process flow scheme shown in Fig. 8 is similar to conventional once-through
hydrocarbon Penex and zeolitic isomerization units. The fresh C5–C6 feed is
combined with makeup and recycle hydrogen and directed to the charge heat
exchanger, where the reactants are heated to the reaction temperature. A fired
heater is not required in the Par-Isom process, because of the much lower reaction
temperature needed with the PI-244 catalyst than with zeolitic catalysts. Hot oil or
steam can be used as the heat source in this exchanger. The heated combined feed is
then sent to the isomerization reactor.
Either one or two reactors can be used in series, depending on the specific
application. Two reactors obtain the best performance from the process but at a
higher capital and additional catalyst inventory costs. In a two-reactor system, the
first reactor is operated at higher temperature (200–220  C) to improve the reaction
Isomerization in Petroleum Processing 493

Makeup Gas

Stabilizer
Offgas

Reactor Product
Separator

Reactor
Feed Stabilizer
Bottoms

Fig. 8 Par-Isom unit process flow scheme

rate, and the second reactor is operated at a lower temperature to take advantage of
the more favorable equilibrium distribution of higher-octane isomers. Two reactors
are generally specified for the Par-Isom process, but a single reactor can be
employed to reduce the capital and operating cost of the unit, but with a small
debit in performance.
The reactor effluent is cooled and sent to a product separator, where the recycle
hydrogen is separated from the other products and returned to the reactor section.
The liquid product is sent to a stabilizer column, where the light ends and dissolved
hydrogen are removed. The stabilized isomerate product can be sent directly to
gasoline blending. In recycle flow schemes, either molecular sieve or fractionation
options are used to separate the lower-octane isomers for recycling to the reactor.
The selection of the separation scheme depends on the feed composition, availabil-
ity of utilities, and the product octane desired.
The higher activity of the PI-244 catalyst makes it an ideal candidate for
revamps of existing zeolitic isomerization units to achieve higher capacity or for
revamps of idle process units, such as fixed-bed reformers or hydrotreaters to
isomerization service. The reactors, recycle compressor, stabilizer, separator, and
most heat exchangers can be employed in the new process flow scheme. The
integration of a Par-Isom reactor into an existing semi-regenerative reforming
unit can be a particularly attractive revamp opportunity for economically adding
isomerization capacity to a refinery. A simple flow scheme illustrating the inte-
grated units is shown in Fig. 9. In this configuration, a new Par-Isom reactor and
charge heater are added to operate in parallel with the existing reforming unit
reactors. A capacity increase can be realized by addition of another reactor in series.
The hydrogen required for the Par-Isom reactor is typically obtained from a
reforming unit recycle compressor, combined with the light-naphtha charge, and
sent to the Par-Isom reactor. The Par-Isom reactor effluent is typically returned to
the reforming unit. The integrated units share a common product condenser,
product separator, and stabilizer to minimize capital and operating costs.
494 D. Sullivan et al.

Net
Hydrogen

Recycle
Compressor

Heavy Stabilizer
Naphtha Offgas
Feed Reforming Product
Reactors Separator

Stabilizer
Charge Column
Heater
Par-Isom
Light Reactor
Naphtha
Feed Stabilizer
Bottoms

Fig. 9 Par-Isom and reforming unit revamp flow scheme

Isomerization Process Economics

The performance and economics of typical Penex and Par-Isom processes, with and
without a DIH column and hydrocarbon recycle, are compared in Table 4. The case
study is for a 10,000 BPD unit with a 10 X-factor feed, which is considered a light
feed. X-factor is a measure of C7+ hydrocarbons, C6 naphthenes, and benzene.
This case study shows that a 10,000 BPD unit can produce 83.4 RON and 81,040
octane barrels with either process technology in a hydrocarbon once-through
configuration (e.g., OT). C5+ yields are well above 95 % in both cases. There
will, however, be differences in quantity of catalyst required, space velocity,
hydrogen to hydrocarbon ratio, and other parameters. It can be noted from the
table that the total investment costs (US Gulf Coast basis) for a Penex-type unit are
about 10 % higher than Par-Isom in this configuration and requires almost twice the
utilities. Utilities included steam, electricity, and hydrogen for both units and
chloriding agent (PERC) and caustic in the Penex unit.
Table 4 also contains comparative data for the same feed type and capacity case,
except with the addition of a DIH column and hydrocarbon recycle. The DIH
increases the RON by almost five numbers, from 83.4 to 88.0, and the total octane
barrels by 4 %. The C5+ yields are approximately 95 %. Utilities also increase,
approximately one-third more for the Par-Isom unit, and 80 % more for the Penex
unit with the recycle flow scheme. CAPEX increases from about $36M USD to
$57M USD for adding a DIH to the Penex unit, whereas the CAPEX increases from
$33M USD to $47M USD for the Par-Isom technology. The investment costs are
less in both cases, in favor of the Par-Isom process for a given configuration.
Chlorided alumina-type catalysts have lower density (approximately half) and
typically cost less from a total investment perspective, but also require added
Isomerization in Petroleum Processing 495

Table 4 Isomerization unit economics for 10,000 BPD unit with a 10 X-factor (light) feed
Units Penex OT Par-Isom OT Penex-DIH Par-Isom-DIH
Feed rate BPD 10,000 10,000 10,000 10,000
RONC 83.4 83.4 88.0 88.0
Octane barrels 81,040 81,040 84,520 84,500
Total CAPEX $MM 36.5 32.7 56.9 47.5
Utilities Base Base  0.56 Base  1.82 Base  1.36
1. CAPEX based upon the US Gulf Coast prices 2014
2. Utilities are expressed on a relative basis, as costs vary on a regional basis
3. Utilities include fuel gas, electricity, hydrogen, steam (+ chloriding agents + caustic for Penex)
OT once-through hydrocarbon, DIH deisohexanizer

utilities such as a chloriding agent and caustic. After all variables are considered,
the return on investment and profitability can be about equal for both technologies
for a new unit for this particular case study (e.g., C5–C6 feed with a 10 X-factor), for
either configuration, with or without a DIH.
While the total investment costs are higher with a DIH recycle for either
technology, it is often selected for cases where higher octane is needed in a
refinery’s gasoline pool, particularly when complying with clean fuel specifications
in some markets.
Processes based on chlorided alumina catalysts have historically been most
popular due to an activity advantage, but advances in sulfated zirconia technology
has closed the gap, making both choices viable. However, chlorided alumina
catalysts provide greater flexibility in some applications; they can handle C5–C6
feeds with higher benzene content and X-factor and provide higher conversion for
feeds that partially contain, or are based on, C4 hydrocarbons. It is important that
any processor conduct a full techno-economic evaluation of process types and
configuration, considering refinery and market objectives.

Catalyst Suppliers

For detailed up-to-date lists of catalysts and suppliers, the Oil and Gas Journal
periodically publishes a comprehensive review. The main suppliers of light-
naphtha isomerization catalyst are currently Albemarle, Axens IFP Group, GTC,
and Honeywell UOP.

Conclusions

Light-naphtha isomerization technology, introduced in the 1930s, has undergone

numerous advances to the process flow scheme and catalyst design over the course
of history, and we expect to see continued interest and development in this field.
The isomerization process has become increasingly important in helping refiners
496 D. Sullivan et al.

improve the octane of pentane- and hexane-rich naphtha and to meet the clean fuel
specifications, including low-benzene-content gasoline. It has also been critical to
provide isobutane to produce motor fuel alkylate as a high-octane blending com-
ponent. The discussion in this chapter has been based on technology development
and the relative performance of UOP’s catalysts, particularly since UOP was a
pioneer in this field and continues its technical leadership position today. Similar
conclusions could be drawn if using equivalent catalysts and process technology
from other suppliers.
Two process options are available via either chlorided alumina-type catalysts
(e.g., Penex process with I-82) or sulfated zirconia catalyst (e.g., Par-Isom process
with PI-244). Both provide excellent upgrading of light naphtha with respect to
octane number, yield, and total octane barrels. Addition of a recycle system with
DIH further increases the octane number and octane barrels, which is important for
meeting growing clean fuel specifications. A full techno-economic assessment is
required for final technology selection for a given application based on refinery and
market objectives.
Revamping existing fixed-bed isomerization, hydrotreating, or semi-
regenerative reforming units to Par-Isom-type process is an economical way to
repurpose existing assets to meet octane and clean fuel demand. In most cases, the
revamp can be accomplished with minimal changes to existing equipment. The
high activity of the PI-244 catalyst can result in up to 4 RON higher-octane
isomerate than can be achieved with zeolitic catalysts as well as higher throughput
in revamp situations.

References
IHS CERA. Annual Long-Term Strategic Workbook, Refining and Product Markets (IHS CERA,
Cambridge, MA 2014) Germany
Euro Fuel Specifications. Website: http://ec.europa.eu/environment/air/transport/fuel.htm
C.D. Gosling, R.R. Rosin, P. Bullen, T. Shimizu, T. Imai, Revamp opportunities for isomerization
units. Petroleum Techonology Quarterly, Vol. 3, pp. 55–59 (1998)
Physical Constants of Hydrocarbons C3-C10, ASTM Committee D-2 on Petroleum Products and
Lubricants and API Research Project 44 on Hydrocarbons and Related Compounds, American
Society of Testing Materials, (1971)
H. Pines, The Chemistry of Catalytic Hydrocarbon Conversion (Academic, New York, 1981),
pp. 12–18
C. Remsberg, H. Higdon, Ideas for Rent: The UOP Story, Library of Congress Catalog Card
No. 94-60759, (1994)
R. van Santen, in Catalysis: From Principles to Applications, 1st edn., ed. by M. Beller,
A. Renken, R. van Santen (Wiley-VCH, Germany 2012), pp. 139–143
D. Shecterle, Options for Gasoline Pool Benzene Management, AiChE Ch 16, (2008). Web: http://
www.aiche-fpd.org/listing/16.pdf
D.R. Stull, E.F. Westrom Jr., G.C. Sinke, The Chemical Thermodynamics of Organic Compounds
(Robert E. Krieger, Malabar, 1987)
US EPA MSAT program regulations, 40 CFR 80 subpart, (2014). Web: http://www.epa.gov/otaq/
fuels/gasolinefuels/MSAT/index.htm
Isomerization in Petroleum Processing 497

Further Reading
N.A. Cusher et al., Isomerization for Future Gasoline Requirements, Proceedings of the NPRA
Annual Meeting, 25–27 Mar 1990
R.A. Meyers, Handbook of Petroleum Refining Processes, 2nd edn. (McGraw-Hill, New York,
1996)
C.L. Moy et al., Benzene Reduction for Reformulated Gasoline, Proceedings of the AIChE Spring
National Meeting, 29 Mar–2 Apr 1992
A.S. Zarchy et al., Impact of Desulfurization on the Performance of Zeolite Isomerization
Catalysts, Proceedings of the AIChE Annual Meeting, 11–16 Nov 1990