Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 9.5
UOP PAR-ISOM PROCESS
Nelson A. Cusher
UOP LLC
Des Plaines, Illinois

Light straight-run (LSR) naphtha fractions are predominantly C5’s and C6’s. Some C7’s are
also present. They are highly paraffinic and have clear research octane numbers (RONC)
usually in the 60s. This fraction, which constitutes 10 percent of a typical gasoline pool in
the United States, is usually upgraded with paraffin isomerization technology.
The use of paraffin isomerization technology to upgrade the octane of light naphtha
streams has been known to the refining industry for many years and has gained importance
since the onset of the worldwide reduction in the use of lead antiknock compounds and
benzene. This technology continues to be important in view of current U.S. and European
legislation on reformulated gasoline.
The most cost-effective means to upgrade an LSR feedstock in a grassroots situation is
the UOP* Penex* process. This process relies on a highly active chlorided alumina cata-
lyst to produce an isomerate product with a RONC of 82 to 85. However, the catalyst is
sensitive to contaminants and is not regenerable.
Alternatively, refiners with idle processing equipment such as old catalytic reformers
or hydrodesulfurization units can consider converting this equipment to the UOP Once-
Through (O-T) Zeolitic Isomerization process (formerly known as the Shell Hysomer†
process). These conversions can be accomplished quickly and at low cost to provide a 10
to 12 octane number increase for the light naphtha. Zeolitic catalysts are tolerant of con-
taminants and are regenerable, but operate at relatively high temperatures that limit the
maximum octane that can be achieved.
With the commercialization of the UOP Par-Isom process, the refiner has another
option for light paraffin isomerization. The key to this new process is the LPI-100 catalyst,
an innovative, high-performance sulfated metal oxide catalyst with activity approaching
that of chlorided alumina catalysts, but with the benefit of being both robust and regener-
able. The basic formulation for LPI-100 catalyst was originally developed by Cosmo
Research Institute and Mitsubishi Heavy Industries in Japan. With the UOP Par-Isom
process, an LSR feedstock can be upgraded to 79 to 82 RONC.

*UOP, Penex, Par-Isom, LPI-100, and HS-10 are service marks and/or trademarks of UOP.
† Hysomer is a service mark and/or trademark of Shell Oil.

9.41
Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)
Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
Any use is subject to the Terms of Use as given at the website.
 UOP PAR-ISOM PROCESS

9.42 ISOMERIZATION

PROCESS DISCUSSION

The UOP Par-Isom process is specifically designed for the catalytic isomerization of pen-
tanes, hexanes, and mixtures thereof. The reactions take place in the presence of hydrogen,
over a fixed bed of catalyst, and at operating conditions that promote isomerization and
minimize hydrocracking. The unit operates at moderate temperature and pressure.
Ideally, an isomerization catalyst would convert all the feed paraffins to the high-
octane-number branched structures: nC5 to isopentane and nC6 to 2,2- and 2,3-dimethylbu-
tane. These reactions are controlled by a thermodynamic equilibrium that is more
favorable at low temperature. The Penex process operates at a lower temperature than the
Par-Isom process, which in turn operates at a lower temperature than the Once-Through
Zeolitic Isomerization process. Consequently, the Penex process produces the highest
product octane, followed by the Par-Isom process, with the Once-Through Zeolitic
Isomerization process offering the lowest product octane.
Table 9.5.1 shows typical charge and product compositions for a C5-C6 Par-Isom unit.
With C5 paraffins, interconversion of normal pentane and isopentane occurs. The C6 paraf-
fin isomerization is somewhat more complex. Since the formation of 2- and 3-methylpen-

TABLE 9.5.1 Typical Estimated Performance, Par-Isom Isomerization

Unit 10,000 BPD

Hydrogen consumption 1,602,000 SCF/day

Light-gas yield
C1 137,000 SCF/day
C2 67,000 SCF/day
C3 246,000 SCF/day
Component Fresh feed to reactor Product
Flow rate, BPD
IC4 10 278
NC4 58 135
IC5 1,684 3,185
NC5 2,907 1,368
Cyclo-C5 169 169
2,2-Dimethylbutane 51 984
2,3-Dimethylbutane 193 461
2-Methylpentane 1,208 1,555
3-Methylpentante 880 903
NC6 1,935 572
Methylcyclopentane 195 216
Cyclo-C6 341 121
Benzene 175 0
C7 194 86
Total 10,000 10,033
C4⫹ properties:
Specific gravity 0.659 0.647
Reid vapor pressure, kg/cm2 (lb/in2 absolute) 0.8 (10.8) 1.0 (14.6)
Octane number
RONC, clear 68.1 81.8
RONC ⫹ 3 cm3 tetraethyl lead/U.S. gal 88.4 97.1
MONC, clear 66.4 79.9
MONC ⫹ 3 cm3 tetraethyl lead/U.S. gal 87.3 97.8

Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)

Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
Any use is subject to the Terms of Use as given at the website.
 UOP PAR-ISOM PROCESS

UOP PAR-ISOM PROCESS 9.43

tane and 2,3-dimethylbutane is limited by equilibrium, the net reaction involves mainly the
conversion of normal hexane to 2,2-dimethylbutane. All the feed benzene is hydrogener-
ated to cyclohexane, and a thermodynamic equilibrium is established between methylcy-
clopentane and cyclohexane. The octane rating shows an increase of some 13.7 numbers.

PROCESS FLOW SCHEME

The Par-Isom process flow scheme is shown in Fig. 9.5.1 and is identical to the O-T
Zeolitic Isomerization process flow scheme. In fact, since the two processes operate over
the same pressure range, LPI-100 catalyst is a drop-in replacement for HS-10 catalyst that
results in a 2 to 3 octane number improvement.
The light naphtha feed is combined with makeup and recycle hydrogen before being
directed to the charge heater where the reactants are heated to reaction temperature. A fired
heater is not required in the Par-Isom process, due to the much lower reaction temperature
needed for LPI-100 catalyst than for zeolitic catalysts. Hot oil or high-pressure steam can
be used as the heat source in this exchanger. The heated combined feed is then sent to the
isomerization reactor.
The reactor effluent is cooled and then sent to a product separator where the recycle
hydrogen is separated from the other products. Recovered recycle hydrogen is directed to
the recycle compressor and then returned to the reaction section. The liquid product is sent
to a stabilizer column where the light ends and dissolved hydrogen are removed. The sta-
bilized isomerate product can be sent directly to gasoline blending.
Alternatively, the stabilizer bottoms can be fractionated in a deisohexanizer column to
concentrate the normal hexane and low-octane methylpentanes into a sidecut stream. This
sidecut stream combines with the fresh feed before entering the Par-Isom reactor. The
deisohexanizer column overhead, which is primarily isopentane, 2,2-dimethylbutane, and
2,3-dimethylbutane, is recovered for gasoline blending. A small bottoms drag stream, con-
sisting of C6 naphthenes and C7’s, is also removed from the deisohexanizer column and
used for gasoline blending or as reformer feed. Product octanes in the range of 85 to 87
RONC can be achieved with this flow scheme.

Makeup gas
Off
Stabilizer
Gas

Product
Separator

Rx

Reactor
Feed Stabilizer
Bottoms
FIGURE 9.5.1 Par-Isom process flow scheme.

Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)

Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
Any use is subject to the Terms of Use as given at the website.
 UOP PAR-ISOM PROCESS

9.44 ISOMERIZATION

CATALYST INFORMATION

Sulfated metal oxide catalysts can be considered to be solid superacids and exhibit high
activity for paraffin isomerization reactions. Sulfated metal oxide catalysts form the basis
of the new generation of isomerization catalysts that have been actively discussed in the
scientific literature in recent years. These catalysts are most commonly tin oxide (SnO2),
zirconium oxide (ZrO2), titanium oxide (TiO2), or ferric oxide (Fe2O3) that have been sul-
fated by the addition of sulfuric acid or ammonium sulfate. Sulfated alumina is not an
active catalyst for hydrocarbon reactions.
Sulfated metal oxide catalysts have now been commercialized with the introduction of
UOP’s LPI-100 catalyst. Activity of this new catalyst is considerably higher than that of
traditional zeolitic catalysts, equivalent to about 85°C (150°F) lower reaction temperature.
The lower reaction temperature allows for significantly higher product octane, about 82
RONC for a typical feed or 3 numbers higher than a zeolitic catalyst. LPI-100 catalyst is
robust and is not permanently deactivated by water or oxygenates in the feedstock. It is
also fully regenerable by using a simple oxidation procedure that is comparable to that
practiced for zeolitic catalysts. The high activity of the sulfated metal oxide catalyst makes
it an ideal candidate for (1) revamping existing zeolitic isomerization units for higher
capacity, (2) revamping idle hydrotreaters and reformers for isomerization service, or (3)
new units where the full performance advantage of chlorided alumina catalysts is not
required or where catalyst stability due to feedstock contaminants is a concern.

COMMERCIAL INFORMATION

As of 2002, eight Par-Isom units have been commissioned that process between 900 and
7500 BPD of feed. Three additional units are in the design/construction phase.
Table 9.5.2 provides a summary of Par-Isom investment costs and utility requirements.
Information is provided for a grassroots unit. Note that no new major equipment is
required when an O-T Zeolitic Isomerization unit is converted to an O-T Par-Isom unit of
the same feed capacity.

WASTES AND EMISSIONS

No wastes or emissions are created by the Par-Isom* process. Product stabilization, howev-
er, does result in small amounts of liquefied petroleum gas (LPG) (C3 ⫹ C4, rich in IC4) and
stabilizer overhead (H2 ⫹ C1 ⫹ C2) products. The stabilizer overhead products are usually
used as fuel. The LPG is a valuable by-product that is blended elsewhere in the refinery.

Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)

Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
Any use is subject to the Terms of Use as given at the website.
 UOP PAR-ISOM PROCESS

UOP PAR-ISOM PROCESS 9.45

TABLE 9.5.2 O-T Par-Isom Process Economics and Performance

Economics
New unit cost, $/BPSD 870
Utilities, per BPSD feed
Electric power (new unit only), kW 0.07
Fuel consumed (conversion only @ 90%
efficiency), kcal/h (Btu/h) 61 (240)
Water 17°C rise, m3/day (gal/min) 0.16 (0.03)
MP steam, kg/h (lb/h) 0.46 (1.00)
LP steam, kg/h (lb/h) 0.55 (1.21)
Hydrogen consumption, m3/day (SCF/h) 2.7–6.1 (4–9)
Typical performance
Isomerate research octane number, clear 79–82
C5⫹ isomerate yield, LV % 97–98
Catalyst expected life, years 5–10
Basis: Battery limits; U.S. Gulf Coast, 2002; 10,000 BPSD
feed, including stabilizer

Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)

Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
Any use is subject to the Terms of Use as given at the website.
 UOP PAR-ISOM PROCESS

Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com)

Copyright © 2004 The McGraw-Hill Companies. All rights reserved.
Any use is subject to the Terms of Use as given at the website.