Petroleum Refining Engineering
Upgrading Naphtha
Gasoline Stabilization
Objective
• Gasoline containing high C3 and C4 results
in:
1. High vapour pressure (explosion hazard)
2. Losses on storage
3. May cause vapour locking
• C3 and C4 have to be removed either by:
1. Refrigeration of the tower
2. High pressure distillation (stabilization)
Objective
• The pressure to be used is calculated such
that the top product is a saturated liquid at
the condenser temperature
• Increase in pressure causes:
1. Relative volatility is reduced
2. Relatively small amount of vapors to pass
through the tower
• N.B.: Stabilizers have smaller diameters
Scheme A
Scheme B
Which is better?
• Scheme B is preferred because gasoline
(consisting of the high volume) was kept at
atmospheric pressure so the separation is
conducted at lower cost.
Upgrading Naphtha
Objective
• Gasoline is produced by blending several
different refinery streams – butanes,
straight-run gasoline, reformate, alkylate,
isomerate, FCC gasoline, and others.
• This section gives an overview of the
processes that either upgrade or generate
gasoline blend stocks.
Upgrading Naphtha
Isomerization
Catalytic Oligomerization
Alkylation
Isomerization
Isomerization Objectives
• In Refining, when we say “isomerization
process,” we are referring specifically to
the on-purpose isomerization of n-butane,
n-pentane, and n-hexane.
• The main purpose of n-paraffin
isomerization is to produce isoparaffins
with substantially higher octane numbers.
Isomerization Objectives
• Isomerization process is of great importance in
petroleum refineries as:
1. The process is valuable in converting n-butane
into iso -butane , which can be alkylated to liquid
hydrocarbons in the gasoline boiling range.
2. The process can be used to increase the octane
number of the paraffins , boiling in the gasoline
boiling range, by converting some of the
n-paraffins present into iso -paraffins.
Isomerization of Normal Paraffins to
Isoparaffins
Isomerization of Alkylcyclopentanes to
Cyclohexanes, plus subsequent conversion
to Benzene
Isomerization in a Nutshell
Isomerization Catalysts
• The process involves contact of the hydrocarbon and a
catalyst under conditions favorable to good product
recovery.
• The most common catalyst for isomerizing n-butane is
platinum (Pt) on alumina promoted by chloride.
• The high activity of this catalyst allows operation at
relatively low temperature. Is this useful ?
• Yes as the high activity of this catalyst allows operation
at relatively low temperature. This is beneficial because
the reaction is controlled by equilibrium; at low
temperature, equilibrium favors isobutane.
• Pt/alumina catalysts can’t be regenerated, and they are
highly sensitive to water and other contaminants.
Isomerization Catalysts
• In units that isomerize n-pentane and n-hexane, the
reactions are catalyzed either by Pt/alumina or Pt on
zeolite.
• The zeolite catalysts require higher temperatures, but they
are less sensitive to water. As with butane isomerization, the
reactions are controlled by equilibrium, so lower reaction
temperatures favor branched isomers. Which is better ?
• The high temperatures required by zeolite catalysts reduce
the octane of the product relative to products made at
lower temperatures with chlorided alumina catalysts.
• Both are very reactive and can lead to undesirable side
reactions such as cracking and olefin formation.
• These undesired reactions are controlled by such
techniques as the addition of inhibitors to the hydrocarbon
feed or by carrying out the reaction in the presence of
hydrogen.
Process Flow: C4 Isomerization
Process Flow: C4 Isomerization
Application:
• The widely used Butamer process is a high-efficiency, cost
effective means of meeting the demands for the production
of isobutene by isomerizing normal butane (nC4) to
isobutene (iC4)
• Motor-fuel alkylate is one blending component that has
seen a subustantial increase in demand because of its
paraffinic, high-octane, low-vapor pressure blending
properties. Isobutane is a primary feedstock for producing
motor-fuel alkylate.
Process Flow: C4 Isomerization
Description:
• UOP’s innovative hydrogen-once-through (HOT) Butamer
process results in substantial savings in capital equipment and
utility costs by eliminating the need for a product separator or
recycle-gas compressor.
• Typically, two reactors, in series flow, are used to achieve high
onstream efficiency. The catalyst can be replaced in one
reactor while operation continues in the other. The stabilizer
separates the light gas from the reactor effluent.
• A Butamer unit can be integrated with an alkylation unit. In
this application, the Butamer unit feed is a side-cut from an
isostripper column, and the stabilized isomerate is returned to
the isostripper column.
• Unconverted n-butane is recycled to the Butamer unit, along
with n-butane from the fresh feed. Virtually complete
conversion of n-butane to isobutene can be achieved.
Process Flow: C4 Isomerization
Feed:
• The best feeds for a Butamer unit contain the highest practical
n-butane content, and only small amounts of isobutene,
pentanes and heavier material. Natural gas liquids (NGL) from a
UOP NGL recovery unit can be processed in a Butamer unit.
Yield:
• The stabilized isomerate is a near-equilibrium mixture of
isobutene and n-butane with small amounts of heavier
material. The light-ends yield from cracking is less than 1 wt%
of the butane feed.
Installation:
• More than 70 Butamer units have been commissioned, and
additional units are in design or construction.
• Butamer unit feed capacities range from 800 to 35,000+ bpsd
(74 to 3,250 tpd)
C5C6 Isomerization
Process Flow: C5 /C6 Isomerization
Application
• The Par-Isom process is an innovative application
using high-performance nonchlorided-alumina
catalysts for light-naphtha isomerization.
• The process uses PI-242 catalyst, which approaches
the activity of chloride alumina catalysts without
requiring organic chloride injection.
• The catalyst is regenerable and is sulphur and water
tolerant
Process Flow: C5 /C6 Isomerization
Description
• The fresh C5/C6 feed is combined with make-up and recycle
hydrogen which is directed to a charge heater, where the
reactants are heated to reaction temperature.
• The heated combined feed is then sent to the reactor. Either
one or two reactors can be used in series, depending on the
specific application.
• The reactor effluent is cooled and sent to a product separator
where the recycle hydrogen is separated from other products.
• Recovered recycle hydrogen is directed to the recycle
compressor and back to the reaction section.
• Liquid product is sent to a stabilizer column where light ends
and any dissolved hydrogen are removed.
• The stabilized isomerate product can be sent directly to
gasoline blending.
Process Flow: C5 /C6 Isomerization
Feed
• Typical feed sources for the Par-Isom process include
hydro-treated light straight-run naphtha, light natural
gasoline or condensate and light raffinate from benzene
extraction units.
• Water and oxygenates at concentrations of typical
hydro-treated naphtha are not determintal, although
free water in the feedstock must be avoided.
• Sulfur suppresses activity, as expected, for any noble-
metal based catalyst. However, the suppression effect is
fully reversible by subsequent processing with clean
feedstocks.
Process Flow: C5 /C6 Isomerization
Yield
• Typical C5+ yields 97 wt% of the fresh feed.
• The product octane is 81 to 87, depending on the flow
configuration and feedstock qualities.
Installation
• The first commercial Par-Isom process unit was placed
in operation in 1996.
• There are currently 10 units in operation.
• The first commercial application of PI-242 catalyst was
in 2003, and the unit has demonstrated successful
performance meeting all expectations.
UOP Penex process
• Penex process is the primary isomerization
technology for upgrading C5/C6 straight run naphtha
• The reaction takes place in the presence of hydrogen
with a platinum catalyst, and the reactor conditions
are selected so that catalyst life is long and
regeneration is not required.
• The reaction conditions promote isomerization and
minimize hydrocracking.
• It results in savings in the capital equipment and
utility cost by eliminating the product separator and
the recycle gas compressor.
UOP Penex process
Process Flow: C5C6 Isomerization
Application
• Most of the implanted legislation requires limiting
benzene concentration in the gasoline pool.
• This has increased the demand for high-performance
C5 and C6 naphtha isomerization technology because
of its ability to reduce the benzene concentration in
the gasoline pool while maintain or increasing the
pool octane.
• The Penex process has served as the primary
isomerization technology for upgrading C5 / C6 light
straight-run naphtha.
Process Flow: C5C6 Isomerization
Description
• 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 charge
heater before entering the reactors.
• The reaction conditions promote isomerization and minimize
hydrocracking.
• Two reactors are present in series ,the feed flows first to a
saturation reactor, which removes olefins and (to a large
extent) benzene.
• After saturation, the feed goes to an isomerization reactor,
where normal paraffins are converted to iso-paraffins.
Process Flow
• The reactor effluent is cooled before entering the product
stabilizer.
• In new Penex designs, both the recycle gas compressor
and the product separator have been eliminated.
• Only a slight excess of hydrogen above chemical
consumption is used.
• The makeup hydrogen, which can be of any reasonable
purity, is typically provided by a catalytic reformer.
• 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 bottom
of the column then passes to gasoline blending.
Process Flow Cont.
• Alternatively, the stabilizer bottoms can be separated
into normal and iso-paraffin components by
fractionation or molecular-sieve separation or a
combination of the two methods to obtain recycle of
the normal paraffins and low-octane methyl-pentanes
(MeC5).
• Product octanes in the range of 87 to 92 RON, clear, can
be achieved by selecting one of the various possible
schemes.
• Many configurations of separation equipment are
possible, as discussed in the next slides.
• The optimum arrangement depends on the specific
charge stock composition and the required product
octane number.
UOP Penex Standard Flow Options
a) MeC5 and nC6 Recycle Option
UOP Penex Standard Flow Options
a) MeC5 and nC6 Recycle Option:
• The least capital-intensive recycle flow scheme is
achieved by combining the Penex process with a
deisohexanizer column.
• The deisohexanizer column concentrates the low
octane methyl-pentanes into the side-cut stream.
• This side-cut stream combines with the fresh feed
before entering the Penex reactor.
• The deisohexanizer column overhead, which is
primarily iso-pentane, 2,2-dimethylbutane, and 2,3-
dimethylbutane, is recovered for gasoline blending.
• A small bottoms drag stream, consisting of C6
naphthenes and C7’s, is also removed from the
deisohexanizer column and used for gasoline
blending or as reformer feed.
UOP Penex Standard Flow Options
b) nC5 and nC6 Recycle via UOP Molex Option
UOP Penex Standard Flow Options
b) nC5 and nC6 Recycle via UOP Molex Option
• An efficient recycle operation is obtained by
combining the Penex process with UOP’s
Molex* process, which uses molecular sieves
to separate the stabilized Penex product into a
high-octane iso-paraffin stream and a low-
octane normal paraffin stream.
• In this system, fresh feed together with the
recovered low-octane normal paraffin stream is
charged to the Penex unit.
• The isomerized product is de-normalized in the
Molex unit and recovered for gasoline blending.
UOP Penex Standard Flow Options
c) nC5, nC6 and MeC5 Recycle Option
Process Flow: C5C6 Isomerization
Products
• For typical C5 / C6 feeds, equilibrium will limit the
product to 83 to 86 RONC on a single hydrocarbon pass
basis.
• To achieve higher octane, UOP offers several schemes in
which lower octane components are separated from
the reactor effluent and recycled back to the reactors.
These recycle modes of operation can lead to product
octane as high as 93 RONC, depending on feed quality.
Process Flow: C5C6 Isomerization
Feed
• Penex process can process feeds with high levels of C6
cyclics and C7 components. In addition, feeds with
substantial levels of benzene can be processed without
the need for a separate saturation section
Installation
• UOP is the leading world-wide provider of isomerization
technology.
• More than 120 Penex units are in operation. Capacities
range from 1,000 bspd to more than 25,000 bpsd of
fresh feed capacity.
