Design a De-Iso Hexanizer (DIH) for a

Isomerization Unit to boost RON from 82-84

to 90-93 of Gasoline by using Light Naphtha
ISOMERIZATION:
The isomerization process upgrades the octane number of light naphtha fractions and also
simultaneously reduces benzene content by saturation of the benzene fraction. Isomerization is a
simple and cost-effective process for octane enhancement compared with other octane-improving
processes. Isomerate product contains very low sulfur and benzene, making it ideal blending
component in refinery gasoline pool. Due to the significance of isomerization to the modern
refining industry, it becomes essential to review the process with respect to catalysts, catalyst
poisons, reactions, thermodynamics, and process developments
The octane numbers of the LSR naphtha [C5-180oF (C5-82oC)] can be improved by the use of an
isomerization process to convert normal paraffins to their isomers.This results in significant
octane increases as n-pentane has an unleaded (clear) RON of 61.7 and isopentane has a rating of
92.3. In once-through isomerization where the normal and iso compounds come essentially to
thermodynamic equilibrium, the unleaded RON of LSR naphtha can be increased from 70 to
about 8284. If the normal components are recycled, the resulting research octane numbers will
be about 8793 RONC
Thereby the development of isomerization process is one of the effective methods for
solution of this problem. It allows the producing of commercial gasoline which corresponds to
the current and perspective requirements to the fuels and provides necessary flexibility of
processing.
TYPES OF ISOMERIZATION PROCESSES
Three types of industrial isomerization processes are worked out currently:
high-temperature isomerization process (360-440 ) on fluorinated-alumina catalysts;
medium-temperature isomerization process (250-300 ) on zeolite catalysts;
low-temperature isomerization process on chlorinated-alumina catalysts (120-180 )
and sulfated metal oxides (180-210 ).
LIGHT NAPHTHA:
Light naphtha is the fraction boiling between 30 C and 90 C and consists of molecules with 56
carbon atoms. It is the virgin heavy naphtha that is usually processed in a catalytic reformer
because the light naphtha has molecules with 6 or less carbon atoms which, when reformed, tend to
crack into butane and lower molecular weight hydrocarbons which are not useful as high-octane
gasoline blending components. Also, the molecules with 6 carbon atoms tend to form aromatics
which is undesirable because governmental environmental regulations in a number of countries
limit the amount of aromatics (most particularly benzene) that gasoline may contain.

PENEX PROCESS:
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. The Penex process is a fixed-bed
procedure that uses high activity chloride-promoted catalysts to isomerize C5/C6 paraffins to
higher octane branched components. The reaction is conducted in the presence of a minor amount
of hydrogen. Even though the chloride is converted to hydrogen chloride, carbon steel construction
is used successfully because of the dry environment. For typical C5/C6 feeds, equilibrium will
limit the product to 83 to 86 RON (Research Octane Number) on a single hydrocarbon pass basis.
To achieve higher octane, UOP offers several schemes in which lower octane components are
separated and recycled back to the reactors. These recycle modes of operation can lead to product
octane as high as 93 RON.
 Hydrocarbon Once-through the light naphtha passes through the isomerization reactor
only once. Normal paraffins are converted to iso paraffins but the conversion is limited by
equilibrium. Typical product octanes are in the 80-84 RONC range.
Isomerization/DIH A de-isohexanizer is used to recover and recycle unconverted
normal hexane and low octane hexane isomers to the reactor system. RONC values of 87-
89 can be achieved.
DIP/Isomerization/Super DIH Using a de-isopentanizer upstream of the Isomerization
reactor to remove isopentane and a de-ioshexanizer downstream to recover and recycle low
octane hexanes, RONC values of 90-93 can be achieved.
PENEX/MOLEX:
The Molex process is an adsorptive separation method that utilizes molecular sieves for the
separation of n-paraffins from branched and cyclic hydrocarbons. The separation is 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 phase, heating, cooling and power
requirements are remarkably low. Sorbex is the name applied to a particular technique developed
by UOP for separating a component or group of components from a mixture in the liquid phase by
selective adsorption on a solid adsorbent.

Feed to Product Comparison

Other Comparison
LIGHT NAPHTHA ISOMERIZATION CATALYSTS:
There are three different commercial catalyst types for light naphtha isomerization: zeolitic
catalyst,amorphous chlorided alumina catalyst, and sulfated zirconia catalyst. These catalyst
types differ by the chemistry of the acid function. Light naphtha isomerization units carry out
many different reactions, many of which require a metal function. All of the commercial
isomerization catalysts include platinum in the formulation to create metal function. Platinum is
preferred for its sulfur tolerance. With platinum, sulfur is not a permanent poison since it can be
stripped.

Isomerization of paraffins in C5/C6 streams is an equilibrium limited reaction where branched

paraffin isomers are generally favored by low temperatures. The most active catalysts, capable
of operating at the lowest temperatures, will produce the highest octane products.

ZEOLITIC CATALYSTS:
Zeolitic catalysts have the lowest activity of the isomerization catalysts, so must operate at the
highest temperatures. High temperature operation results in lower product octane due to less
favorable equilibrium for branched paraffins. In addition to operating at high temperatures,
zeolitic catalysts are the least selective isomerization catalysts, giving lower product yields.The
main benefit of zeolitic catalysts is that they are not permanently deactivated bywater or other
oxygenates and are fully regenerable.

CHLORIDED ALUMINA CATALYSTS:

Amorphous chlorided alumina catalysts,are the most active light naphtha isomerization catalysts
currently available. Their high activity meansthat they operate at the lowest isomerization
temperatures and thus achieve the highest octane productsand highest yields. However, these
catalysts are permanently deactivated by oxygenate compounds, likewater and CO, so feed and
makeup gas driers are needed. Well maintained driers can facilitate a longcatalyst life, in excess
of 10 years. Process units designed for chlorided alumina catalysts also requirecontinuous
chloride injection to maintain high activity. These catalysts are not regenerable.

Chlorided alumina catalysts are irreversibly deactivated when acid sites are converted by
oxygenates.Catalysts with the highest acid site densities will have the longest catalyst life.

SULFATED ZIRCONIA CATALYSTS:

Sulfated zirconia catalysts are tolerant of moderate levels of oxygenates inthe feed and in the
makeup gas, like water and CO, eliminating the need for driers. These catalysts do notrequire a
halide promoter, so there is no chloride injection or caustic scrubber. Sulfated zirconia
catalystsare fully regenerable using a simple oxidation procedure comparable to the procedure
used for zeolitic based isomerization catalysts.
BENZENE SATURATION CATALYSTS:
For saturation of benzene in light naphthas, the most commonly used catalysts are either nickel
or platinum based catalysts.

Platinum-based catalysts are not permanently poisoned by sulfur upsets and will saturate benzene
with very little cracking of the naphthato light ends, consuming minimal hydrogen.

REFERENCES:

1. NPTEL, Isomerization,
(file:///D:/Project/NPTEL%20%20Chemical%20Engineering%20%20Petroleum%20Refi
nery%20Engineering.html) 24/September/2013. Retrieved on 28/February/2017

2. WikiPedia,Light Naphtha, (https://en.wikipedia.org/wiki/Petroleum_naphtha). Retrived

on 28/February/2017

3. Honeywell UOP, Gasoline,

(https://www.uop.com/processingsolutions/refining/gasoline/#naphtha-isomerization) .
Retrived on 28/February/2017

4. M.F Muhamed, W.M Shehata Improving gasoline quality produced from light naphtha
(Egyptian Journal of Petroleum), 21-Feb-2016

5. http://www.tandfonline.com/doi/full/10.1080/10916466.2010.504931?scroll=top&needA
ccess=true (22-February-2017,1:30pm)