Catalytic Isomerization

A. General Process

Isomerization is the process in which light straight chain paraffins of low RON (C6, C5
and C4) are transformed with proper catalyst into branched chains with the same carbon
number and high octane numbers. The hydro treated naphtha (HTN) is fractionated into
heavy naphtha between 90 to 190 oC (190–380 oF) which is used as a feed to the reforming
unit. Light naphtha C5 80 oC (180 oF) is used as a feed to the isomerization unit. There are
two reasons for this fractionation: the first is that light hydrocarbons tend to hydrocrack in the
reformer. The second is that C6 hydrocarbons tend to form benzene in the reformer. Gasoline
specifications require a very low value of benzene due to its carcinogenic effect (Travers,
2001).

Isomerization is a reversible and slightly exothermic reaction:

N-paraffin ƒ „ i-paraffin

The conversion to iso-paraffin is not complete since the reaction is equilibrium conversion
limited. It does not depend on pressure, but it can be increased by lowering the temperature.
However operating at low temperatures will decrease the reaction rate. For this reason a very
active catalyst must be used.

There are two types of isomerization catalysts: the standard Pt/chlorinated alumina
with high chlorine content, which is considered quite active, and the Pt/zeolite catalyst. This
bi-functional nature catalyst consists of highly chlorinated alumina (8–15 w% Cl2)
responsible for the acidic function of the catalyst. Platinum is deposited (0.3–0.5 wt%) on the
alumina matrix. Platinum in the presence of hydrogen will prevent coke deposition, thus
ensuring high catalyst activity. The reaction is performed at low temperature at about 130 oC
(266 oF) to improve the equilibrium yield and to lower chlorine elution. The standard
isomerization catalyst is sensitive to impurities such as water and sulphur traces which will
poison the catalyst and lower its activity. For this reason, the feed must be hydro treated
before isomerization. Furthermore, carbon tetrachloride must be injected into the feed to
activate the catalyst. The pressure of the hydrogen in the reactor will result in the elution of
chlorine from the catalyst as hydrogen chloride. For all these reasons, the zeolite catalyst,
which is resistant to impurities, was developed.
Zeolites are crystallized silica-aluminates that are used to give an acidic function to
the catalyst. Metallic particles of platinum are impregnated on the surface of zeolites and act
as hydrogen transfer centers. The zeolite catalyst can resist impurities and does not require
feed pretreatment, but it does have lower activity and thus the reaction must be performed at
a higher temperature of 250 oC (482 oF). A comparison of the operating conditions for the
alumina and zeolite processes is shown in Table 1.

Table 1: Comparison of operating conditions using different type of catalyst

Operating Conditions Pt/chlorine Alumina Pt/Zeolite Catalyst
Catalyst
o
Temperature ( C) 120 – 180 250 – 270
Pressure (psi) 20 – 30 15 – 30
Space velocity (h-1) 1–2 1–2
H2/HC Ratio (mol/mol) 0.1 – 2 2–4
Product RON 83 – 84 78 – 80

The isomerate yield from light naphtha isomerization is usually very high (> 97 wt. %).
Typical yields are given in Table 2.

Table 2: Typical yield of isomerate from isomerization process

Component Yield (%)
C3 0.348
iC4 0.619
nC4 1.770
C5+ 97.261

B. Once-Through (O-T) Zeolitic Isomerization Process Technology

The O-T Zeolitic Isomerization process is a fixed-bed, vapor-phase process for the
catalytic isomerization of low-octane normal pentane or normal hexane or both to high-
octane iso paraffins. The isomerization reaction is carried out at 245 to 270°C (470 to 520°F)
and 21 to 35 kg/cm2 (300 to 500 psi gage) in the presence of hydrogen. Equipment
requirements are a reactor vessel, heater, recycle hydrogen compressor, feed-product heat
exchanger, product cooler, phase separator drum, and product stabilizer section. The catalyst
used in the O-T Zeolitic Isomerization process is based on a strongly acidic zeolite with a
recoverable noble-metal component. No external acid activators are used and the catalyst
does not produce a corrosive environment. Therefore, feed drying is not necessary. No wastes
or emissions are created by the O-T Zeolitic Isomerization. Product stabilization, however,
does result in small amounts of LPG (C3 + C4, rich in iC4) and in stabilizer vent (H2 + C1 +
C2) products. The stabilizer vent products are usually used as fuel. The LPG is a valuable by-
product that is blended elsewhere in the refinery. With all these reasons, this process
technology have more sustainable value compared to conventional isomerization process
which using reformer unit. The sustainable design description and process flow diagram is
shown in Table 3 and Figure 1 respectively.

Table 3: Sustainable design description of each equipment used in the process technology
Equipment Sustainable Design Description
Reactors  With catalytic reformers that were originally designed for a
weight hourly space velocity (WHSV) comparable to that of the
O-T Zeolitic Isomerization process, no major modifications to the
reactors are required except to eliminate inter-stage heating.
 Because of the difference in feed densities, the O-T Zeolitic
Isomerization catalyst requirement is typically about 20 percent
less than the reformer catalyst requirement.
 If the O-T Zeolitic Isomerization unit is to be designed for a
lower WHSV or if recycle of normal paraffins to obtain the
maximum octane increase is desired, converting from internal to
external insulation can achieve about a 25 to 30 percent increase
in reactor volume. This increase is possible because of the
relatively low operating temperature for the O-T Zeolitic
Isomerization process; however, the material used to construct
the reactor shell should be checked for pressure or temperature
limitations.
Compressors  The recycle-compressor capacity for a reformer is usually more
 than adequate for the O-T Zeolitic Isomerization process. A 25
kg/cm2 (350 psi gage) reformer will have about twice the
capacity required for the O-T Zeolitic Isomerization process.
 In plants containing two compressors, each with a 50 percent
capacity, one compressor can be shut down.
 Makeup hydrogen for the O-T Zeolitic Isomerization process can
be reformer net gas. If the reformer supplying the hydrogen is a
low-pressure unit, a small makeup compressor is required. For an
O-T Zeolitic Isomerization unit processing 5000 barrels per day
(BPD) of feed, hydrogen makeup is typically about 500,000
standard cubic feet per day (SCF/day).
Heaters and Heat  Heat exchange equipment and heaters are usually more than
Exchangers adequate. Inter-stage reheaters between reactors are not required
because the isomerization reaction is mildly exothermic.
Feed Pump (Optional)  Because of differences in feed gravity, feed rate, vapor pressure,
and possible net positive suction head (NPSH), a new feed pump
may be required.
Stabilizer System  In the O-T Zeolitic Isomerization process, the amount of light
ends produced is substantially less than in the reforming process.
 In any case, where a reformer has been converted to an O-T
Zeolitic Isomerization unit, the stabilizer feed rate is higher even
though the stabilizer overhead product is lower than in the
reforming operation.
 The small amount of light ends plus a bottoms product with a
higher vapor pressure may dictate an increased reflux rate or a
column retray or both.
Feed to H2 ratio
H2 Recycle Gas
4:1

FEED LPG
nC5+

Saturated Steam
MAKE UP H2

T = 245 – 270oC FIXED BED

P = 300 – 500 psi REACTOR RECYCLE STABILIZER
Pt/Zeolite Catalyst COMPRESSOR

H2

Water (17oC)

PHASE ISOMERATE
Mixture SEPARATOR
iC5+

Isomerate + LPG

Figure 1: Process Flow Diagram of Zeolitic Isomerization Process Technology

 The need for a high-octane product to replace the octane lost with lead phase-out and
benzene reduction in the gasoline pool has placed more emphasis on isomerization. As
sustainability value previously noted, another value of this technology is the flexibility of the
process technology can be adapted to an existing idle hydrotreater, catalytic reformer, or
other hydro-processing unit with minimal investment. The actual time to modify a unit ranges
from a few days to a few weeks. Paraffin isomerization is limited by thermodynamic
equilibrium so that a once-through, or single-pass, isomerization reactor provides only partial
conversion of the normal paraffins. In the reactor, C 5-C6 paraffins are isomerized to a near-
equilibrium mixture, and aromatics become saturated to naphthenes, which, in turn, are
partially converted into paraffins. Olefins in the feed are saturated, and C 7+ paraffins are
mostly hydrocracked to C3 to C6 paraffins.

Tables 4 and 5 provide a summary of typical O-T Zeolitic Isomerization yields,

product properties, conversion costs, utility requirements, and overall operating costs. Typical
C5+ isomerate yield is 97 to 98 liquid volume percent (LV %) on feed and the octane number
is increased by about 10 to 12, resulting in an isomerate quality of 77 to 80 RONC. Usually
no new major equipment is required when a reformer is converted to an O-T Zeolitic
Isomerization unit of the same feed capacity. Thus, the only costs are for new piping and
instrumentation, engineering, and a charge of O-T Zeolitic Isomerization catalyst. For a unit
with a feed rate of 5000 BPD, capital costs will total $3.0 to $4.5 million. This amount is only
about half of the cost of a grassroots installation. Expected catalyst life is 10 to 15 years.

Table 4: Typical Estimated Performance, O-T Zeolitic Isomerization Unit, 10,000 BPD
Components Fresh Feed to Reactor Product
Hydrogen consumption, m3/h (1000 2018 (1710) -
SCF/day)
Light gas yield, m3/h (1000 SCF/day)
C1 - 333 (283)
C2 - 180 (152)
C3 - 292 (248)
C4+ streams, LV % on feed:
iC4 0.10 2.50
nC4 0.58 1.41
iC5 16.84 30.39
nC5 29.07 16.17
Cyclo-C5 1.69 1.24
2,2-dimethylbutane 0.51 8.26
2,3-dimethylbutane 1.93 3.74
2-methylpentane 12.08 14.43
3-methylpentane 8.80 9.21
nC6 19.35 8.24
Methylcyclopentane 1.95 3.35
Cyclo-C6 3.41 0.96
Benzene 1.75 0.0
C7 1.94 0.97
Total 100.0 100.87
C4+ properties:
Specific gravity 0.659 0.648
Reid vapor pressure, kg/cm3 (psi) 0.8 (10.8) 1.0 (14.2)
Octane number:
RON, clear 68.1 79.5
RON + 3 cm3 TEL/U.S. gal 88.4 95.5
MON, clear 66.4 77.6
MON + 3 cm3 TEL/U.S. gal 87.3 96.3

Table 5: O-T Zeolitic Isomerization Conversion Economics and Performance

(Basis: Battery limits; U.S. Gulf Coast, 2001, 4000–6000 BPSD, including new stabilizer,
new piping and instrumentation, engineering, and catalyst)
Total capital required, $/BPSD 750
Utilities, per BPSD feed:
Fuel consumed (90% efficiency), million 0.0006 (0.0025)
kcal/h (million Btu/h)
Water at 17°C rise, m3/day (gal/min) 0.33 (0.06)
Power, kWh 0.05
Steam at 10.5 kg/cm2 (150 psi gage), 0.5 (1.1)
saturated, kg/h (lb/h)
Hydrogen consumption, m3/day (SCF/h) 2.7 – 6.1 (4 – 9)
Typical performance:
Isomerate, RONC 77 – 80
C5+ isomerate yield, LV % 97 – 98
Catalyst expected life, years 10 – 15