UNIT -3: FRACTIONATION OF PETROLEUM

The petroleum refining industry converts crude oil into more than 2500 refined products,
including liquefied petroleum gas, gasoline, kerosene, aviation fuel, diesel fuel, fuel oils,
lubricating oils, and feedstocks for the petrochemical industry. Petroleum refinery activities
start with receipt of crude for storage at the refinery, include all petroleum handling and
refining operations, and they terminate with storage preparatory to shipping the refined
products from the refinery.
The petroleum refining industry employs a wide variety of processes. A refinerys processing
flow scheme is largely determined by the composition of the crude oil feedstock and the
chosen slate of petroleum products. The example refinery flow scheme presented in Figure
shows the general processing arrangement used by refineries in general. The arrangement of
these processes will vary among refineries, and few, if any, employ all of these processes.
The refinery processes are classified into the following categories.

1. Separation processes
a. Atmospheric distillation
b. Vacuum distillation
c. Light ends recovery (gas processing)
The first phase in petroleum refining operations is the separation of crude oil into its major
constituents using 3 petroleum separation processes: atmospheric distillation, vacuum
distillation, and light ends recovery (gas processing). Crude oil consists of a mixture of
hydrocarbon compounds including paraffinic, naphthenic, and aromatic hydrocarbons with
small amounts of impurities including sulfur, nitrogen, oxygen, and metals. Refinery
separation processes separate these crude oil constituents into common boiling-point
fractions.
2. Petroleum conversion processes
a. Cracking (thermal and catalytic)
b. Reforming
c. Alkylation
d. Polymerization

e. Isomerisation
f. Coking
g. Visbreaking

To meet the demands for high-octane gasoline, jet fuel, and diesel fuel, components such as
residual oils, fuel oils, and light ends are converted to gasoline and other light fractions.
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Cracking, coking, and visbreaking processes are used to break large petroleum molecules into
smaller ones. Polymerization and alkylation processes are used to combine small petroleum
molecules into larger ones. Isomerisation and reforming processes are applied to rearrange
the structure of petroleum molecules to produce higher-value molecules of a similar
molecular size.

3. Petroleum treating processes

a. Hydro desulfurization
b. Hydro treating
c. Chemical sweetening

d. Acid gas removal

e. Deasphalting

Petroleum treating processes stabilize and upgrade petroleum products by separating them
from less desirable products and by removing objectionable elements. Undesirable elements
such as sulfur, nitrogen, and oxygen are removed by hydro desulfurization, hydro treating,
chemical sweetening, and acid gas removal. Treating processes, employed primarily for the
separation of petroleum products, include such processes as deasphalting. Desalting is used to
remove salt, minerals, grit, and water from crude oil feedstocks before refining. Asphalt
blowing is used for polymerizing and stabilizing asphalt to improve its weathering
characteristics

4. Feedstock and product handling

a. Storage
b. Blending

c. Loading
d. Unloading

5. Auxiliary facilities
a. Boilers
b. Waste water treatment
c. Hydrogen production
d. Sulfur recovery plant
e. Cooling towers
f. Blow down system
g. Compressor engines

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A wide assortment of processes and equipment not directly involved in the refining of crude
oil is used in functions vital to the operation of the refinery. Examples are boilers, waste
water treatment facilities, hydrogen plants, cooling towers, and sulfur recovery units.
Products from auxiliary facilities (clean water, steam, and process heat) are required by most
process units throughout the refinery.

ATMOSPHERIC DISTILLATION UNIT :

Process description
The first process encountered in any conventional Refinery is the Atmospheric Crude
Distillation Unit. In this unit the crude oil is distilled to produce distillate streams which will
be the basic streams for the refinery product slate. These streams will either be subject to
further treating downstream or become feed stock for conversion units that may be in the
Refinery Configuration. A schematic flow diagram of an atmospheric crude unit is shown in
Figure

Crude oil is pumped from storage to be heated by exchange against hot overhead and product
side streams in the Crude Unit. At a preheat temperature of about 200250F water is
injected into the crude to dissolve salt that is usually present. The mixture enters a desalter
drum usually containing an electrostatic precipitator. The salt water contained in the crude is
separated by means of this electrostatic precipitation. The water phase from the drum is sent
to a sourwater stripper to be cleaned before disposal to the oily water sewer. It must be
understood however that this de-salting does not remove the organic chlorides which
may be present in the feed. This will be discussed later when dealing with the towers
overhead system. The crude oil leaves the desalter drum and enters a surge drum. Some of the
light ends and any entrained water are flashed off in this drum and routed directly to the
distillation tower flash zone (they do not pass through to the heater). The crude distillation
booster pump takes suction from this drum and delivers the desalted crude under flow control
to the fired heater via the remaining heat exchange train. On leaving heat exchanger train, the
crude oil is heated in a fired heater to a temperature that will vaporize the distillate products
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in the crude tower. Some additional heat is added to the crude to vaporize about 5% more

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than required for the distillate streams. This is called over flash and is used to ensure good

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reflux streams in the tower. The heated crude enters the fractionation tower in a lower section

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called the flash zone. The unvaporized portion of the crude leaves the bottom of the tower via

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a steam stripper section, while the distillate vapors move up the tower counter current to a

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cooler liquid reflux stream. Heat and mass transfer take place on the fractionating trays

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contained in this section of the tower above the flash zone. Distillate products are removed

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from selected trays (draw-off trays) in this section of the tower. These streams are stream

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stripped and sent to storage. The full naphtha vapor is allowed to leave the top of the tower to
be condensed and collected in the overhead drum. A portion of this stream is returned as
reflux while the remainder is delivered to the light end processes for stabilizing and further
distillation.

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A Pump around section is included at the light gas oil draw off. This is simply an
internal condenser which takes heat out of that section of the tower. This in turn ensures a
continued reflux stream flow below that section. The product side streams are stripped free of
entrained light ends in separate stripping towers. These towers also contain fractionation trays
(usually four but sometimes as many as six) and the side stream drawn off the main tower
enters the top tray of its respective stripper. Steam is injected below the bottom tray and
moves up the tower to leave at the top, together with the light ends strip out, and is returned
to the main fractionator at a point directly above the side stream draw-off tray. These side
stream stripper towers are usually stacked one above the other in a single column in such a
way as to allow free flow from the side stream draw-off tray to its stripper tower. On a few
occasions, where the particular side stream specification requires it, the stripping may be
effected by reboiling instead of using steam. One such requirement maybe in the Kero side
stream if this stream is to be routed directly into jet fuel blending and therefore must be dry.
The residue (unvaporized portion of the crude) leaves the flash zone to flow over four
stripping trays counter current to the flow of stripping steam. This stripping steam enters the
tower below the bottom stripping tray. Its purpose primarily is to strip the residue free of
entrained light ends. The fact that this steam enters the flash zone it also enhances the
flashing of the crude in this zone by creating a reduced partial pressure for the liquid/vapor
separation. This becomes an important factor in the design and operation of the atmospheric
crude distillation unit. The stripped residue leaves the bottom of the unit to be routed either
through the units heat exchanger system and the to product storage or hot to some down
stream processing unit such as a vacuum distillation unit or a thermal cracker.

Vacuum Distillation Unit (VDU)

The atmospheric residue is further distilled to provide the heavy distillate streams used for
producing lube oil or as feed to conversion units. This distillation however has to be
conducted under sub atmospheric pressure conditions. The temperature required for
vaporising the residue at atmospheric pressure would be too high and the crude would crack.
The process follows very much the same pattern as the atmospheric distillation. Should the
cold feed be pumped from storage, it is heat exchanged against hot product and pump around
streams before being vaporised in the distillation unit heater. Normally though the feed is
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pumped hot directly from the CDUs residue stripper to the vacuum units heater. Thereafter
the distillate vapours are condensed in the tower by heat and mass transfer with the cold
reflux streams moving down the tower in the same way as the side streams in the
Atmospheric unit. The products are taken off at the appropriate sections are cooled either by
heat exchange with colder streams in the atmospheric unit, by air coolers or, in some cases as
heating mediums to light end reboiler. They are then pumped to storage. Neither the vacuum
residue that leaves the bottom of the tower in this process nor the side-streams are steam
stripped. The vacuum condition is produced by steam ejectors taking suction from the top of
the tower. These ejectors remove inert and other vapour that may exist and pull a vacuum of
about 5 mm HG absolute. The tower internals are usually expanded grid type which offer low
pressure drop such that the flash zone pressure is about 2530
30 mmHg absolute

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BLENDING
Gasoline or diesel blending is a complex refining process as operating personnel are required
to meet fuel quality and legislative targets while operating at the lowest possible cost. To
meet these operating targets, typical properties that are measured and controlled include
RON, MON, RVP, aromatics, benzene, olefins, ASTM-D86 distillation points, and
oxygenates for gasoline, and for diesel, cetane index, cloud point, pour point and ASTM-D86
distillation or recovery points. Traditionally, these measurements have been obtained by
periodically stopping the blend and removing samples to the laboratory, or have been
provided by a host of classical on-line analytical techniques, e.g. Octane Engines and Gas
Chromatographs. There are, however, a number of problems associated with these
approaches. These include the high capital and operating costs of multiple techniques, slow
response time and, in many cases, poor analytical repeatability. These disadvantages are
especially evident in the utilization of octane engines. These performance issues can lead to
significantly higher blending costs due to unavoidable property giveaway, as well as
reduced blender throughput, coupled with increased inventory and demurrage costs. The
financial incentive to blend continuously and faster is therefore very significant, which means
that rapid on-line analysis of key product properties is highly desirable.
GASOLINE ADDITIVES
Additives are gasoline-soluble chemicals mixed with gasoline to enhance certain performance
characteristics or to provide characteristics not inherent in the gasoline. Typically, they are
derived from petroleum-based raw materials and their function and chemistry are highly
specialized. They produce the desired effect at the parts-per-million (ppm) concentration
range. (One ppm is 0.0001 mass percent or 1mg/kg.)
Oxidation inhibitors, including aromatic amines and hindered phenols, are also called
antioxidants. They prevent gasoline components from reacting with oxygen in the air to form
peroxides or gums. They are needed in virtually all gasolines but especially in those with high
olefin content. Peroxides can degrade antiknock quality, cause fuel pump wear, and attack
plastic or elastomeric fuel system parts. Soluble gums can lead to engine deposits, and
insoluble gums can plug fuel filters. Inhibiting oxidation is particularly important for fuel
used in modern fuel-injected vehicles because those with fuel recirculation design may
subject the fuel to more temperature and oxygen-exposure stress.

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Corrosion inhibitors are carboxylic acids and carboxylates. The tank and pipeline facilities
of gasoline distribution and marketing systems are constructed primarily of uncoated steel.
Corrosion inhibitors help prevent free water in gasoline from rusting or corroding these
facilities. Corrosion inhibitors are less important once gasoline is in a vehicle. The metal parts
in the fuel systems of todays vehicles are made of corrosion-resistant alloys or of steel that is
covered with a corrosion-resistant coating. More plastic and elastomeric parts are replacing
metal parts in fuel systems. In addition, service station systems and operations are designed to
help prevent free water from being delivered to vehicle fuel tanks.
Silver corrosion inhibitors are substituted thiadiazole. Combinations of trace amounts of
elemental sulfur, hydrogen sulfide, and mercaptans can cause the silver used in vehicle fuel
gauge sender units to corrode and fail. Silver corrosion inhibitors, also referred to as filmers,
inhibit the corrosion caused by active sulfur compounds.
Metal deactivators are chelating agents, that is, chemical compounds that capture specific
metal ions. The more active metals such as copper and zinc effectively catalyze the oxidation
of gasoline. These metals are not used in most gasoline distribution and vehicle fuel systems,
but when they are present, metal deactivators inhibit their catalytic activity.
Demulsifiers are polyglycol derivatives. An emulsion is a stable mixture of two mutually
insoluble materials. A gasoline/water emulsion can be formed when gasoline passes through
the high-shear field of a centrifugal pump if the gasoline is contaminated with free water.
Demulsifiers improve the water-separating characteristics of gasoline by preventing the
formation of stable emulsions.
Antiknock compounds increase the antiknock quality of gasoline. They include materials
based on:
Lead alkyls, such as tetraethyl lead (TEL) and tetramethyl lead (TML)
Manganese, called methylcyclopentadienyl manganese tricarbonyl (MMT)
Iron, called ferrocene
Because only a small amount of additive is needed, using antiknock compounds is a lowercost method to increase octane number than changing gasoline chemistry. Gasoline
containing TEL was first marketed in 1923. The average concentration of lead in gasoline
gradually was increased until it reached a maximum of about 660 milligrams per liter (mg/L)
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or 2.5 grams per gallon (g/gal) in the late 1960s. After that, a series of events resulted in the
use of less lead. First, new refining processes produced higher-octane gasoline components.
Then, the population of vehicles that require unleaded gasoline those with catalytic exhaust
emission controls steadily grew. Last, U.S. EPA regulations required the reduction of the
lead content of gasoline in phased steps beginning in 1979. The U.S. EPA completely banned
the addition of lead additives to on-road gasoline in 1996. Currently, the amount of incidental
lead may not exceed 13.2 mg/L (0.05 g/gal) and cannot be deliberately added.
Anti-icing additives are surfactants, alcohols, and glycols. They prevent ice formation in the
carburetor and fuel system (see page 4). The need for this additive is disappearing as
oldermodel vehicles with carburetors are replaced by vehicles with fuel injection systems.
Dyes are oil-soluble solids and liquids used to visually distinguish batches, grades, or
applications of gasoline products. For example, gasoline for general aviation, which is
manufactured to unique and exacting requirements, is dyed blue to distinguish it from motor
gasoline.
Markers are a means of distinguishing specific batches of gasoline without providing an
obvious visual clue. A refiner may add a marker to its gasoline so it can be identified as it
moves through the distribution system.
Drag reducers are high-molecular-weight polymers that improve the fluid flow
characteristics of low-viscosity petroleum products. As energy costs have increased, pipelines
have sought more efficient ways to ship products. Drag reducers lower pumping costs by
reducing friction between flowing gasoline and pipe walls

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