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Isomerization Technique
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CHAPTER 2
ISOMERIZATION TECHNIQUE
The Penex process has served as the primary isomerization technology for upgrading
C5/C6 light straight-run naphtha feeds since UOP introduced it in 1958. This process has
a wide range of operating configurations for optimum design flexibility and feedstock
processing capabilities.
The Penex process is a fixed-bed procedure that uses high activity chloride-promoted
reaction is conducted in the presence of a minor amount of hydrogen. Even though the
because of the dry environment. For typical C5/C6 feeds, equilibrium will limit the
The operating conditions are such that promote isomerization and minimize
Ideally, this isomerization catalyst would convert all the feed paraffins to the high octane-
number branched structures: normal pentane (nC5) to isopentane (iC5) and normal
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Equipments Used in Penex Process:
• Methanator
•Regenerant evaporator
• Chloride drum
• Reactors (2 in number)
• Stabilizer column
• Stabilizer re-boiler
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• Stabilizer overhead air cooler
• Caustic tank
• Water Tank
Equipment:
Hydro treated SR light naphtha at temperature 45 0C & pressure 4.5 kg/cm2 is passed
through driers to control moisture at 1.0 ppmw in the feed. Drying medium is the
molecular sieves. There are two drier, one remain in operation while the other is on
regeneration. Isomerate is used as regenerant. Dry liquid feed is collected in feed surge
drum. Molecular sieves are regenerated by isomerate & there replacement depends on the
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efficiency or after period of four year.
Make up gas is dry by passing into dryers. Molecular sieves used as drying agents. Dry
gas is control at moisture < 1.0 ppmv. Before drying of gas CO & CO2 isremoved from
the makeup gas. It is accomplished by passing the gas through Methanator. CO & CO2
are converted into methane in presence of Nickel oxide catalyst. Nickel catalyst cannot be
regenerated. It is replaced totally; its life is 4-5 years. Temperature & pressure of
Combine liquid feed & make up gas is heated in pre-heat exchangers & chloride is
injected before entering the reactors. The Reactor System is typically designed to operate
at a minimum pressure of 31.6 Kg/cm2 (g). Lead reactor inlet temperatures range from
131°C to 200°C and lag reactor inlet temperatures range from 142°C to 186°C.
H2/HCBN mole ratio is maintained as 0.20 at reactors inlet & 0.05 at reactors outlet.
Reactor effluents passed through stabilizer where lighter gases & propane is separated
from the isomerate. Stabilizer column is operated at temperature 145 °C & pressure 18.0
kg/cm2.
The purpose of net gas scrubbers is that to neutralize the net gas prior sending to fuel gas
header with caustic (strength is 10%wt). Operating parameters of net scrubbers is that
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pressure is 6.5 kg/cm2 and temperature is 45 °C.
capital equipment and utility costs by eliminating product separator and recycle gas
compressor.
Light naphtha feed is charged to one of the two dryer vessels. These vessels are filled
with molecular sieves, which remove water and protect the catalyst. After mixing with
makeup hydrogen, the feed is heat-exchanged against reactor effluent. It then enters a
Typically, two reactors in series are used to achieve high on-stream efficiency. The
catalyst can be replaced in one reactor while operation continues in the other. One
characteristic of the process is that catalyst deactivation begins at the inlet of the first
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Reactor and proceeds slowly as a rather sharp front downward through the bed. The
adverse effect that such deactivation can have on unit on-stream efficiency is avoided by
installing two reactors in series. Each reactor contains 50% of the total required catalyst.
Piping and valving are arranged to permit isolation of the reactor containing the spent
catalyst while the second reactor remains in operation. After the spent catalyst has been
replaced, the relative processing positions of the two reactors are reversed. During the
short time when one reactor is off-line for catalyst replacement, the second reactor is fully
The reactor effluent flows to stabilizer after passing through the heat exchanger. The
stabilizer overhead vapors are caustic scrubbed for removal of the HCl formed from
organic chloride added to the reactor feed to maintain catalyst activity. After scrubbing,
the overhead gas then flows to fuel. The stabilized, isomerized liquid product from the
The Penex process (see below) uses the most active chlorided-alumina catalyst and
operates in the range 120-180°C. overall catalyst cost. At lower LHSVs, more catalyst is
System pressure is another variable and is considered in conjunction with the hydrogen
flow rate to the reactor. Chlorided-alumina is more active at higher pressures. It requires
only a slight excess over stoichiometric hydrogen, since the catalyst does not produce
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Figure 2.2 (Block flow diagram of ―one through process)
To achieve higher octane, UOP offers several schemes in which lower octane components
are separated and recycled back to LHSV is set during the design phase of any
isomerization project and reflects the compromise between residence time and the
reactors. These recycle modes of operation can lead to product octane as high as 93 RON.
hexane, and some C6 cyclics. It is the lowest cost option of the recycle flow schemes &
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2.1.8 Penex Process With Recycle And Fractionation (DIP/Penex
Process/DIH):
Separation and recycle of unconverted normal C5 and C6 paraffins and low octane C6
isoparaffins back to the reactor, produce a higher octane product. The most common flow
some C6 cyclics. It is the lowest capital cost option of the recycle flow schemes and
In the Penex/DIH process the stabilized isomerate is charged to a DIH column producing
an overhead product containing all the C5 and dimethylbutanes. Normal hexane and some
of the methylpentanes are taken as a side-cut and recycled back to the reactors. The small
amount of bottoms (C7+ and some C6 cyclics) can be sent to gasoline blending or to a
reformer
The addition of a deisopentanizer (DIP) or a super DIH will achieve the highest octane
from a fractionation hydrocarbon recycle flow scheme. In this scheme, both low octane
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Figure 2.4 (DIP-Penex-DIH)
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2.2 PROCESS DESCRIPTION:
This flow scheme uses Molex technology for the economic separation and recycle of n-
The Molex process is an adsorptive separation method that utilizes molecular sieves for
effected in the liquid phase under isothermal conditions according to the principles of the
UOP Sorbex separations technology. Because the separation takes place in the liquid
Sorbex is the name applied to a particular technique developed by UOP for separating a
Sorbex is a simulated moving bed adsorption process operating with all process streams
in the liquid phase and at constant temperature within the adsorbent bed. Feed is
introduced and components are adsorbed and separated from each other within the bed. A
separate liquid of different boiling point referred to as ‗desorbent‘ is used todisplace the
feed components from the pores of the adsorbent. Two liquid streams emerge from the
bed – an extract and a raffinate stream, both diluted with desorbent. The desorbent is
removed from both product streams by fractionation and is recycled to the system.
The adsorbent is fixed while the liquid streams flow down through the bed. A shift in the
positions of liquid feed and withdrawal, in the direction of fluid flow through the bed,
simulates the movement of solid in the opposite direction. It is, of course, impossible to
move the liquid feed and withdrawal points continuously. However, approximately the
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same effect can be produced by providing multiple Liquid access lines to the bed, and
periodically switching each net stream to the next adjacent line. A liquid circulating pump
is provided to pump liquid from the bottom outlet to the top inlet of the adsorbent
a) Adsorption
b) Purification
c) Desorption
The adsorbent employed in Molex is a specially prepared molecular sieve with selective
pores. Molex feed enter the adsorbent chamber via rotary valve. Adsorbent chamber is
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2.2.1.2 Purification Operation:
Non-normal paraffins (iso-paraffins) are removed from the adsorption chamber &
purified in raffinate column. Operating temperature & pressure of raffinate column is 125
2.2.1.3 Desorption:
Operating temperature & pressure of the extract column 130 °C & 16.0 kg/cm2.
The performance of the Penex process can be compromised when processing this
generated by the benzene hydrogenation reaction can cause the reactors to operate at
conditions that are less favorable for octane upgrading. For these applications, UOP offers
It includes two reactor sections. The first section is designed to saturate the benzene to
cyclohexane. The second section is designed to isomerize the feed for an overall octane
increase. Each reactor is operated at conditions that favor the intended reactions for
maximum conversion.
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2.3 OCTANE COMPARISON FOR DIFFERENT PROCESSES:
Figure 2.7 (Octane Comparison for different Processes) (Feed RON = 60 to 70)
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