Petroleum

properties

Dr. Hanoon H. Mashkoor &

Asst. Lect. Maryam J. Jaafar
• Isomerization
The process of converting straight paraffins into branched
paraffins is called the isomerization process. Which raises
the octane of light gasoline from (RON 70) to (82RON). It
also revealed the possibility of treating the mixture of
pentane (n - C5) and hexane (n - C6) and converting them
to the branched paraffins. Platinum (Pt) is used as a catalyst
carried on several types of bases such as molecular sieves,
and some chlorides may be added to it in small quantities,
from time to time, to maintain the catalyst activity and the
catalyst can be continued for more than three years before
activation. Usually small amounts of hydrogen are pumped
into the reaction atmosphere to prevent carbon from being
deposited on the surface of the catalyst. The catalyst is
placed in the reactor in the form of a fixed bed.
• Process variables: The temperature, pressure, velocity,
and amount of hydrogen in one way or another affect the
isomerization rate. The temperature used ranges between
(300-400F). However, the lower temperatures are suitable
to reach the chemical equilibrium quickly. As for the
used pressures, they range between (250-400 psig), and
the intermediate velocity ranges between ( 1.5-2.5
LHSV). A ratio of hydrogen to oil is used in mol (2:
1mole ratios).
• Description of the isomerization process:
Before the straight paraffin mixture or light gasoline (C5-
160F, LSR) is pumped into the isomerization unit, it must
first be treated with hydrogen to reduce the sulfur content to
a minimum in order not to cause toxicity to the catalytic
platinum in isomerization. The figure below shows the
flow of materials during the isomerization process, where
the feed material is pumped into the (i - C5) stripper called
(Isopentanizer), where there is no need to treat it. The
straight paraffins are passed from the bottom of the device
onto a desiccator - containing molecular sieves - to adsorb
the water. Then the mixture with dry hydrogen is heated to
(300-400F) and pushed into the fixed bed reactor. The
reaction products cooled ... then the hydrogen was separated
... and it was returned again and mixed with the new feed.
• As for the hydrocarbon products, they are directed to a
stabilizer device to separate the light gases (C3), and the
isomerate product is then taken and directed to the
gasoline pool. The normal pentane (n - C6) may be
separated and returned to the reactor with the new feeder.
• Alkylation's processes: ‫۔‬
The term alkylation in petroleum refining is used for the
reaction of light olefins (C4, C3) with isobutane (i - C4) to
form isoparaffins in the range of gasoline. This means that
the light gases that are usually used as fuel (LPG) can be
converted into more valuable and useful gasoline in this
process. These gases are produced from the processes of
atmospheric distillation, cracking of all kinds, refining, etc.
All of them are suitable as a feedstock for the Alkylatio
process. Sulfuric acid (H2SO4) or hydrofluoric acid (HF)
are used as catalysts.
• Reactions mechanism
The main reactions that take place during the alkylating
process can be summarized as follows:
(1) Propylene (n - C3) interacts with isobutane (i - C4) and
isoheptane (i - C7).
(2) Isobutylene (i - C45) reacts with isobutane (i - C4) to
form isoctane (i - C8).
(3) Propylene (n - C3) can react with isobutane (i - C4) and
form a mixture of propane (n - C4) and isobutylene (i- C4),
then the latter reacts with isobetane (i - C4) to produce
isoctane (i - C8). The products of the reactions are
considered to be of higher octane than the materials involved
in these reactions.
• The catalysts in the Alkylation's processes
Concentrated sulfuric or fluoric acids are used as catalysts to
produce high-octane gasoline called (Alkylate gasoline). The acid
concentration is considered one of the main factors to catalyze
alkylation, as weak acids catalyze the polymerization of olefins -
therefore, it is necessary to maintain a higher concentration of
(88%) for these acids. However, when using a concentration
higher than (99.3%) by weight with respect to sulfuric acid, the
sulfur trioxide gas (S03) sublimates and leads to the formation of
unwanted by-products. When the concentration of the catalytic
acid decreases to less than (80%), part of it must be discarded and
other quantities of the acid with a higher concentration added. Of
course, the strength of the dilute acid must be returned to the
required concentration in special units. Along with acid
concentration, the alkylating processes are affected by
temperature, isobutane (i - C4) concentration, and intermediate
velocity.
• Alkylation with sulfuric acid
The alkylating unit contains the following parts: cooling, reactors,
acid isolation, washing with alkali, and fractionation, as shown in
the chart where sulfuric acid is used as a catalyst, that the best
temperature in which alkylating reactions take place using sulfuric
acid as a catalyst is within limits(4 c) Therefore, the materials
entering the reaction are cooled by the refrigeration equipment and
the olefinic compounds are mixed with isobutane and sulfuric acid
and pumped with a special pump to the refrigeration unit, in which
case all components of the reaction must be in a liquid state and
after that, they enter the reactors and there are mixers inside the
reactors to mix these liquids well mixing to ensure good contact and
efficient mixing between the olefins and isobutane molecules and in
the presence of the acid to achieve the required reaction. After
leaving the reactors, it is sent to the concentration vessel( Acid
Settler) to separate the acid from the reacting petroleum compounds
and withdraw the acid from the bottom of the container to purify it
and
• maintaining its high concentration and returning it to the
reactors again. As for the petroleum compounds coming
out from the top of the sedimentation vessel, they contain
a small amount of acid attached to them and still be
washed with an alkaline substance (caustic soda). Then it
is sent to the fractionation towers in three stages to isolate
the alkali material from the propane, butane, and
isobutane, which is recycled again to the unit. In general,
side reactions occur in the alkylating process, and as a
result, small quantities of propane, butane, and pentane
are formed, and these are not harmful compounds, as it
precipitates with the acid very small amounts of tar (a
heavy brown oil) and disappears when the acid is sent for
purification.
• Alkylation using hydrofluoric acid
This process takes place in a unit containing the Phillips
reactor shown in Fig below. The dry feed material containing
olefins and isobutane (i - C4) is pumped from the bottom of
the vertical tube reaction unit where it is mixed with the
cooled acid. The reaction takes place in the vertical tube at
(70-80F), then the reaction products with the residual acid are
pushed into a separator where the acid is separated and
returned by gravity to the acid cooler, and then mixed with the
new feed in the vertical tube.
As for the hydrocarbon products, they are directed to devices
for separating propane (C3) from butane (C4) and for
gasoline, the product of alkylation. It should be noted that high
temperatures reduce the quality of gasoline.
• Polymerization:
It was found that it is possible to convert small olefins (C3 -
C4) present in petroleum gases to good gasoline by exposing
these practical compounds to polymerize - where the small
molecules collect and give larger molecules - within the
range of gasoline. Polymerization is considered to be less
expensive than alkylation. However, a barrel of gasoline
resulting from polymerization needs about a barrel and a
half of olefins - while the barrel obtained from alkylation
requires only about half of this amount. The main reactions
in polymerization are summarized as follows:‫۔‬
• Two molecules of propane(C3) combine, produce a part of
isohexane (i - C65), two molecules of isobutylene (i - c4)
combine and produce isoactin (i - C85). Solid phosphoric acid
(H3PO4), carried on an inert support, such as ground quartz, is
used as a catalyst. To maintain the catalyst activity for a long
time, the feed should be treated from sulfur compounds, oxygen,
and metal residues before being pushed into the polymerization
unit. Sulfur poisons the acid (catalyst) and oxygen causes the
decomposition of polymerized compounds - that is, it makes the
reaction reverse, and the metal residues neutralize the acid and
make it weak. The acid is consumed at rates between one third to
two thirds of a pound per barrel of product and the reaction takes
place between (300-425F) under pressure. From (400-1500psi),
high pressures are usually used at low temperatures. As for the
intermediate velocity, it is about (0.3gal / Ib).
• The feed material consists of paraffins and light olefins
(C4, C3) .. It must be washed with caustic soda solution
to remove the sulfur compounds (RSH) and then treated
with an amine solution to remove hydrogen sulfide, then
water to remove the soda and amine residues. Then the
feed is dried with silica gel or molecular sieves.
• Process description:
Before pumping the feed into the polymerization reactor,
an amount of water equivalent to (300-400ppm) is added to
activate acid ionization. Then the feed material is heated to
about (40OF) and then it is pumped to the reactor that
contains the catalyst (solid acid) in the form of a fixed bed.
As shown in Figure below. It should be noted that the
polymerization reactions are highly exothermic, so the
temperature is controlled by pumping cold propane. As for
the paraffins in the feeder, they calm the reaction, and thus
its temperature rises above the required rate. The reaction
products are directed to distillation devices to separate
butane and light substances from the polymerized gasoline.
(polymer gasoline)