You are on page 1of 20

Isomerization technologies for the upgrading

of light naphtha and refinery light ends


Dana K. Sullivan, Stephen M. Metro, and Peter R. Pujadó

Outline
1 Introduction

2 History

3 Market trends and regulations

4 Process chemistry of paraffin isomerization

5 Primary reaction pathways

6 Isomerization catalysts

7 Process options

8 Isomerization process flow schemes

9 Process economics

10 Catalyst suppliers

11 Conclusions

12 References

13 Bibliograpy
List of Tables
Table 1 Euro fuel specifications
Table 2 Hydrocarbon octane values
Table 3 Isomerization unit economics for 10,000 BPD unit with a 10X (light) feed
Table 4 Comparison of process requirements for various catalyst types

List of Figures
Figure 1 Isomeration process configurations and octane values
Figure 2 Overall gasoline demand by region
Figure 3 Butane equilibrium
Figure 4 Pentane equilibrium
Figure 5 C6 fraction equilibrium
Figure 6 Penex unit process flow scheme, hydrogen once-through (HOT)
Figure 7 Octane/activity curves for various isomerization catalyst types
Figure 8 Par-Isom unit process flow scheme.
Figure 9 Par-Isom and reforming unit revamp flow scheme
Isomerization technologies for the upgrading
of light naphtha and refinery light ends
Dana K. Sullivan, Stephen M. Metro, and Peter R. Pujadó

1 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
isomerization processes. These regulations include many clean fuels initiatives,
including lead phase out, 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 of
normal butane to iso-butane. Isomerization of C5–C6 paraffins for motor fuel
blending was introduced in the late 1950s.

UOP LLC, a Honeywell company, developed the ButamerTM 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 OleflexTM
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 many important industrial
applications of acid function promoted catalysis. Other examples of the wide
commercial application of acid-catalyzed industrial hydrocarbon reactions are the
alkylation of paraffins and aromatics with olefins, transalkylation and
disproportionation 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.

2 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 co-catalyst (1). 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 ButamerTM 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 iso-
octane molecules with 8 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 post-war 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 the octane by 12 to 20 numbers. This UOP process,
named the PenexTM process, was soon being used in nearly all refineries.

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 improvements
include use of a recycle loop to circulate unreacted hydrocarbons exiting the reactor
back to the reactor inlet and use of fractionators such as a deisopentanizers (DIP) and
deisohexanizers (DIH), and a process section that separates iso- and normal paraffins
via molecular sieve, rerouting the normal paraffins back to the reaction section for
further yield improvements.

Catalyst advances include use of new materials and base formulations to increase
activity, selectivity, and the life of chloride alumina type catalysts. Other catalyst
technologies were developed that didn’t require 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 Figure 1. A
number of technology companies introduced various isomerization catalysts over the
years, including Akzo Nobel NV (now Albemarle), Axens, NPP Neftekhim, Süd-
Chemie AG (now Clariant), Shell Chemicals LP, and UOP (Honeywell UOP LLC).

Figure 1: Isomerization process configurations and octane values

3 Market trends and regulations

3.1 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 additives such as ethanol, used to lower emissions via oxygenate
addition, boost octane and consume a “bio” fuel source, which is typically
produced from corn and sugar cane. Gasoline demand has risen from ~ 20M B/D
in 2000 to 23M B/D in 2013 (2) as per Figure 2. Gasoline demand is expected to
rise to 28M B/D over the next decade as per multiple market forecasting
resources.
Figure 2: Overall gasoline demand by region

About half of the current demand is in developed regions such as North America,
Europe, and Japan (2). Growth has been categorized as flat to declining in these
regions due to 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, Middle East, and Russia, which currently make up
approximately 50% of gasoline demand2, expected to rise by an additional 10%
over the next decade. The drivers for growth include large, growing populations
and economies, 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. Global isomerization capacity is
approximately 2.5 million barrels/day2. While the largest installed capacity is in
North America and Europe, almost 60%, rapid growth is occurring in Russia,
Middle East, and Asia. 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 US and Europe who are “octane
long”, have been operating their isomerization units to primarily saturate benzene
to meet gasoline benzene requirements. Some allow their isomerization catalyst
to deactivate from untreated feed poisoning, but still function to saturate benzene,
using only the catalyst’s metals function.
3.2 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 fuels initiatives, including lead phase-down, minimization of
RVP, 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. A
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 Specifications (3).

Table 1: Euro fuel specifications

Directive EN 228 DIR 98/70 DIR 98/70 DIR 98/70 DIR 98/70
Euro Fuel
Year 1993 1996 2000 2005 2009
Specifications Class Euro I Euro 2 Euro 3 Euro 4 Euro 5
Aromatics Vol % Max No Limit No Limit 42 35 35
Olefins Vol % Max No Limit No Limit 18 18 18
Benzene Vol % Max 5 5 1 1 1
Oxygen Wt % Max 2.5 2.5 2.7 2.7 3.7
Sulfur ppm Max 1000 500 150 50 (10)* 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

In the United States, the Environmental Protection Agency (EPA) sets the fuel
standards, with some variations from state to state, and California is generally
being most stringent. Gasoline specifications are set by CARB, or the California
Air Resource 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 US, the Environmental Protection Agency (EPA)
has implemented a Mobile Source Air Toxics (MSAT) rule to reduce hazardous
air pollutants (4). As of 2011, the EPA requires that refiners must meet a
maximum annual average gasoline benzene content of 0.62 volume %. The
maximum permissible level is 1.3 volume % as of July 2012. These are applied
to US refiners, as well as gasoline imported to the US. There are numerous
technologies available to address lowering benzene content including
prefractionation, saturation, isomerization, and extraction and is a subject of other
literature (5).
The C5 - C6 isomerization unit is typically part of a naphtha complex used to
produce gasoline. The naphtha feed is typically hydrotreated to remove
contaminants 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.

4 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
production 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, 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
nearly 30 numbers higher than n-pentane (6).

Similarly, the multi-branched 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 multi-branched 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 (7). The most active
catalyst, when all other variables are equal, is capable of producing the highest
octane products.
Figure 3 Butane equilibrium

Figure 4 Pentane equilibrium

Figure 5: C6 fraction equilibrium

5 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
CH 3 -CH 2 -CH 2 -CH3  CH 3 -CH 2 -CH = CH 2 + H 2 . (1)
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)):
+
 (2)
CH3 -CH 2 -CH = CH 2 + [H ] [A ]  CH 3 -CH 2 -C H-CH 3 + 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).

(3)
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 (10) (reaction (5)):

(4A)

(4B)

OR
(5)
In addition to these primary reaction pathways, there is evidence indicating the
existence of a bimolecular reaction mechanism, particularly for butane isomerization.
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.

6 Isomerization catalysts
Operation at the lowest temperature results in the formation of the highest octane
product (Table 2 and Figures 3, 4, and 5) in this equilibrium limited reaction. Having
the highest catalyst activity and the lowest operating temperature are 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.

Table 2: Hydrocarbon octane values

Research octane by Motor octane by (R + M )/2


ASTM 2699 ASTM 2700
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

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 (8). 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 application since 1981. The current state of the art
isomerization catalysts are UOP I-82 and I-84 catalysts, and Albemarle’s ATIS-2L,
introduced in the 2000’s, providing higher activity and conversion for C5/ C6
applications.

6.1 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 Figure 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 selectivity 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, dependent 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.
Approximately 85% of the installed isomerization processes today employ
chlorided alumina type catalysts.

6.2 Zeolitic type catalysts


Zeolitic isomerization catalysts, such as UOP’s HS-10 HysomerTM 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 Figure 1. The TIP process uses a multi-vessel vapor phase adsorption process
(IsoSivTM 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
process 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 with zeolitic catalysts, but it is necessary to get the optimum
performance from the catalyst. Approximately 30 zeolitic type units still operate
today.

6.3 Sulfated metal oxide type catalysts


Sulfated metal oxide catalysts, which have been described as solid super acids,
exhibit high activity for paraffin isomerization reactions9 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-IsomTM 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 Figure 7, 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 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.

7 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 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.

Figure 6: Penex unit process flow scheme, hydrogen once-through (HOT)

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 though (OT) configuration and avoid the need for an expensive recycle gas
compressor and loop, it requires continuous chloride addition to maintain
isomerization acid activity, requiring the use of a caustic scrubber neutralize HCl in
the off-gas to eliminate unit corrosion. 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.
Figure 7: Octane/activity curves for various isomerization catalyst types

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 4.

8 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 Figure 8. For simplicity, a once-
through hydrocarbon flow scheme is discussed in this chapter. Recycle hydrocarbon
flow schemes previously developed for naphtha isomerization use either molecular
sieve separation, such as in the TIP process, or fractionation, such as a
deisohexanizer (DIH) column.
Figure 8: Par-Isom unit process flow scheme.

The process flow scheme shown in Figure 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
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 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 recycle to the reactor. The
selection of the separation scheme depends on the feed composition, availability 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-regeneratative reforming unit can be a particularly attractive
revamp opportunity for economically adding isomerization capacity to a refinery. A
simple flow scheme illustrating the integrated units is shown in Figure 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 additional of another reactor in series.

Figure 9: Par-Isom and reforming unit revamp flow scheme

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.

9 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 3. The case
study is for a 10,000 BPD unit with a 10X feed, which is considered a light feed. X-
factor is a measure of C7+ hydrocarbons, C6 naphthenes, and benzene.
Table 3: Isomerization unit economics for 10,000 BPD unit with a 10X (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 x 0.56 base x 1.82 base x 1.36
1) CAPEX based upon US Gulf Coast Prices 2014
2) Utilities are expressed on a relative basis, as costs vary on a reginal basis
3) Utilities include fuel gas, electric, hydrogen, steam (+ chloriding agents + caustic for
Penex)

OT = Once through hydrocarbon DIH = Deisohexanizer


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, electric, and hydrogen for both units, and chloriding agent (PERC)
and caustic in the Penex unit.

Table 4: Comparison of process requirements for various catalyst types

Chlorided Sulfated Zeolitic


Alumina Zirconia
Chemical Injection Chloride None None
Contaminant Sensitivity Yes No No
Dryers +
Equipment Basic Fired Heater
Scrubber
Spent Caustic Stream Yes No No
Heating Medium MP Steam MP Steam Fired Heater
Metallurgy CS CS Alloy
Recycle Compressor No Yes Yes

Table 3 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 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 are lower density (approximately half), and
typically cost less from a total investment perspective, but also require added 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 10X 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.

10 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.

11 Conclusions
Light naphtha isomerization technology, introduced in the 1930’s, 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 improve
octane of pentane and hexane rich naphtha, and to meet the clean fuels
specifications, including low-benzene content gasoline. It has also been critical to
provide iso-butane to produce motor fuel alkyalte as a high octane blending
component. 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 fuels 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 isomerate octane than can be
achieved with zeolitic catalysts as well as higher throughput in revamp situations.

12 References

1. Ideas for Rent: the UOP Story, C.Remsberg and H.Higdon, Library of Congress
Catalog Card No. 94-60759, 1994
2. IHS CERA Annual Long-Term Strategic Workbook, Refining and Product Markets,
2014
3. Euro Fuel Specifications, website:
http://ec.europa.eu/environment/air/transport/fuel.htm
4. US EPA MSAT program regulations, 40 CFR 80 subpart, 2014. Web:
http://www.epa.gov/otaq/fuels/gasolinefuels/MSAT/index.htm
5. D. Shecterle: Options for Gasoline Pool Benzene Management, AiChE Ch 16, 2008,
web: http://www.aiche-fpd.org/listing/16.pdf
6. Physical Constants of Hydrocarbons C3 -C1 0 , 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.
7. D. R. Stull, E. F. Westrom, Jr., and G. C. Sinke, The Chemical Thermodynamics of
Organic Compounds, Robert E. Krieger Publishing Co., Malabar, FL, 1987.
8. H. Pines, The Chemistry of Catalytic Hydrocarbon Conversion, Academic Press, New
York, 1981, pp. 12–18.
9. C. D. Gosling, R. R. Rosin, P. Bullen, T. Shimizu, and T. Imai, Revamp
Opportunities for Isomerization Units, Petroleum Technol. Q. Winter 1997–1998 55–
59.
10. R. van Santen in Catalysis: From Principles to Applications, First Edition, Edited by
M. Beller, A. Renken, and R. van Santen, Wiley-VCH Verlag GmbH & Co. KGaA,
2012, pp. 139-143.

13 Bibliography
N. A. Cusher and others, Isomerization for future gasoline requirements, Proceedings of
the NPRA Annual Meeting, Mar. 25–27, 1990.
R. A. Meyers, Handbook of Petroleum Refining Processes, 2nd ed, McGraw-Hill, New
York, 1996.
A. S. Zarchy and others, Impact of desulfurization on the performance of zeolite
isomerization catalysts, Proceedings of the AIChE Annual Meeting, Nov. 11–16, 1990.
C. L. Moy and others, Benzene reduction for reformulated gasoline, Proceedings of the
AIChE Spring National Meeting, Mar. 29–Apr. 2, 1992.