Distillation

Application
in Petroleum

Distillation
Distillation

separates chemicals by the

difference in how easily they vaporize. The
two major types of classical distillation
include continuous distillation and batch
distillation. Continuous distillation, as the
name says, continuously takes a feed and
separates it into two or more products.
Batch distillation takes on lot (or batch) at
a time of feed and splits it into products by
selectively removing the more volatile
fractions over time.

 Other

ways to categorize distillation

are by the equipment type (trays,
packing), process configuration
(distillation, absorption, stripping,
azeotropic, extractive, complex), or
process type (refining, petrochemical,
chemical, gas treating).

 Many

industries use distillation for

critical separations in making useful
products. These industries include
petroleum refining, beverages,
chemical processing, petrochemicals,
and natural gas processing.

Distillation Categories
System composition
System refers to the chemical
components present in the mixture
being distilled. The two main groups
are binary distillation and
multicomponent distillation.

Binary distillation is a separation of only two

chemicals. A good example is separating ethyl
alcohol (ethanol) from water. Most of the basic
distillation teaching and a lot of theoretical work
starts with looking at binary distillation; it's a lot
simpler.
Multicomponent distillation is the separation of
a mixture of chemicals. A good example is
petroleum refining. Crude oil is a very complex
mixture of hydrocarbons with literally thousands
of different molecules. Nearly all commercial
distillation is multicomponent distillation. The
theory and practice of multicomponent distillation
can be very complex.

Processing Mode

Processing mode refers to the way in which feed

and product are introduced and withdrawn from the
process. Distillation occurs in two modes,
continuous distillation and batch distillation.
Continuous distillation is feed is sent to the still all
the time and product is drawn out at the same
time. The idea in continuous distillation is that the
amount going into the still and the amount leaving
the still should always equal each other at any
given point in time.

Batch distillation is when the amount going into

the still and the amount going out of the still is
not supposed to be the same all the time. The
easiest example to use is like old fashioned spirit
making. The distiller fills a container at the start,
then heats it, as time goes by the vapors are
condensed to make the alcoholic drink. When the
proper quantity of overhead (drink) is made, the
distiller stops the still and empties it out ready for
a new batch. This is only a simple case, in
industrial usage what goes on gets very complex.

Processing Sequence
Fractionation

systems have different

objectives. The major processing objectives
set the system type and the equipment
configuration needed. The common
objectives include removing a light
component from a heavy product, removing
a heavy component from a light product,
making two products, or making more than
two products. We will call these major
categories are called stripping, rectification,
fractionation, and complex fractionation.

 Stripping

systems remove light

material from a heavy product.
Rectification systems remove heavy
material from a light product.
Fractionation systems remove a light
material from a heavy product and a
heavy material from a light product
at the same time.

 Complex

fractionation makes multiple

products from either a single tower or a
complex of towers combined with recycle
streams between them. A good example of
a multiple product tower is a refinery
crude distillation tower making rough cuts
of naphtha (gasoline), kerosene (jet fuel),
and diesel from the same tower. A good
example of a complex tower with internal
recycle streams is a Petlyck (baffle) tower
making three on-specifications products
from the same tower.

System Type
The

behavior of the chemicals in the

system also determines the system
configuration for the objectives. The
three major problems that limit
distillation processes are close-boilers,
distributed keys, and azeotropes.

 Close

boiler systems include chemicals

that boil at temperatures very close to
each other. So many stages of distillation
or so much reflux may be required that the
chemicals cannot be separated
economically. A good example is
separation of nitro-chloro-benzenes. Up to
600 theoretical separation stages with
high reflux may be required to separate
different isomers.
Distributed keys are systems where some
chemicals that we do not want in either
the heavy or the light product boil at a
temperature between the heavy and the
light product.

 Azeotropic

systems are those where

the vapor and the liquid reach the
same composition at some point in
the distillation. No further separation
can occur. Ethanol-water is a perfect
example. Once ethanol composition
reaches 95% (at atmospheric
pressure), no further ethanol
purification is possible.

Reaction
Reactive

distillation uses a reaction

in the distillation equipment to help
the separation. The reaction may or
may not use a catalyst. DMT
manufacture uses reactive distillation
without a catalyst. One process to
make methy-tert-butyl-ether uses a
catalyst inside the distillation tower.
The reaction changes the
composition, allowing the distillation
to work better

Equipment Type
Distillation equipment includes two
major categories, trays and packing.
Trays force a rising vapor to bubble
through a pool of descending liquid.
Packing creates a surface for liquid to
spread on. The thin liquid film has a
high surface area for mass-transfer
between the liquid and vapor.

PETROLEUM
Petroleum

is a complex mixture of
organic liquids called crude oil and
natural gas, which occurs naturally in
the ground and was formed millions of
years ago. Crude oil and natural gas
are of little use in their raw state; their
value lies in what is created from
them: fuels, lubricating oils, waxes,
asphalt, petrochemicals and pipeline
quality natural gas.

HOW OIL WAS FORMED?

Oil

was formed from the remains of

animals and plants that lived millions
of years ago in a marine (water)
environment before the dinosaurs.
Over the years, the remains were
covered by layers of mud. Heat and
pressure from these layers helped the
remains turn into what we today call
crude oil . The word "petroleum"
means "rock oil" or "oil from the
earth."

Where We Get Oil?

The world's top five crude oilproducing countries are:

Saudi Arabia
Russia
United States
Iran
China

Petroleum Hydrocarbon
Structures
Paraffins
Hydrocarbons
Naphthenes

Oil Refining Production

Process
Desalting

and Dewatering
Distillation
Reforming
Cracking
Alkylation
Isomerisation
Polymerisation
Hydrotreating

Desalting and Dewatering

Crude

oil is recovered from the reservoir

mixed with a variety of substances: gases
water and dirt (minerals). Desalting is a
water washing operation performed at the
production field and at the refinery site for
additional crude oil cleanup. If the
petroleum from the seperators contains
water and dirt, water washing can remove
much of the water soluble minerals and
entrained solids. If these crude oil
contaminants are not removed, they can
cause operating problems during refinery
processing, such as equipment plugging and
corrosion as well as catalyst deactivation.

Distillation

The first and the most fundamental step in the refining

process (after the crude oil has been cleaned and any
remnants of brine removed) is distillation, which is often
referred to as the primary refining process. Distillation
involves the separation of the different hydrocarbon
compounds that occur naturally in a crude oil into a number of
different fractions (a fraction is often referred to as a cut). In
the atmospheric distillation process (Fig.), heated crude oil is
separated in a distillation column (distillation tower,
fractionating tower, atmospheric pipe still) into streams that
are then purified, transformed, adapted, and treated in a
number of subsequent refining processes, into products for
the refinery's market. The lighter, more volatile, products
separate out higher up the column, whereas the heavier, less
volatile, products settle out toward the bottom of the
distillation column. The fractions produced in this manner are
known as straight run fractions ranging from (atmospheric
tower) gas, gasoline, and naphtha, to kerosene, gas oils, and
light diesel, and to (vacuum tower) lubricating oil and
residuum.

The feed to a distillation tower is heated by flow

through pipes arranged within a large furnace. The
heating unit is known as a pipe still heater or pipe
still furnace, and the heating unit and the fractional
distillation tower make up the essential parts of a
distillation unit or pipe still. The pipe still furnace
heats the feed to a predetermined temperature
usually a temperature at which a predetermined
portion of the feed will change into vapor. The
vapor is held under pressure in the pipe in the
furnace until it discharges as a foaming stream into
the fractional distillation tower. Here the
unvaporized or liquid portion of the feed descends
to the bottom of the tower to be pumped away as a
bottom nonvolatile product, whereas the vapors
pass up the tower to be fractionated into gas oils,
kerosene, and naphtha.

Reforming
Reforming

is a process which uses

heat, pressure and a catalyst (usually
containing platinum) to bring about
chemical reactions which upgrade
naphthas into high octane petrol and
petrochemical feedstock.

Cracking

Cracking processes break down

heavier hydrocarbon molecules (high
boiling point oils) into lighter
products such as petrol and diesel.
These processes include:
1. catalytic cracking
2. thermal cracking
3. hydrocracking

Alkylation
Alkylation

refers to the chemical

bonding of these light molecules with
isobutane to form larger branchedchain molecules (isoparaffins) that
make high octane petrol.

Isomerisation
Isomerisation

refers to chemical
rearrangement of straight-chain
hydrocarbons (paraffins), so that they
contain branches attached to the main
chain (isoparaffins).

Polymerisation
Under

pressure and temperature, over an

acidic catalyst, light unsaturated
hydrocarbon molecules react and combine
with each other to form larger hydrocarbon
molecules. Such process can be used to
react butenes (olefin molecules with four
carbon atoms) with iso-butane (branched
paraffin molecules, or isoparaffins, with four
carbon atoms) to obtain a high octane
olefinic petrol blending component called
polymer gasoline.

Hydrotreating
Hydrotreating

is one way of removing many

of the contaminants from many of the
intermediate or final products. In the
hydrotreating process, the entering
feedstock is mixed with hydrogen and
heated to 300 - 380oC. The oil combined
with the hydrogen then enters a reactor
loaded with a catalyst which promotes
several reactions:
hydrogen combines with sulphur to form
hydrogen sulphide (H2S) .

Petroleum Products

Aviation Gasoline
Gas Diesel Oil/(Distillate Fuel Oil)
Heavy Fuel Oil Residual
Kerosene
Jet Fuel
LPG
Motor Gasoline
Naphtha
Petroleum Coke
Refinery Gas

Products Made From Oil

InkToysDollsTiresTentsShoesGlueSkisDyesCamerasCombs
DiceMopsPursesDressesPajamasPillowsCandlesBoatsCrayo
nsCaulkingBalloonsCurtainsMilkjugsPuttyTool
racksSlacksYarnRoofingLuggageFanbeltsCarpetingLipstick
AspirinDishwashingliquidsUnbreakabledishesCarsound
insulationMotorcyclehelmetsRefrigeratorliningsElectrician's
tapeRoller-skatewheelsPermanentpressclothesSoftcontact
lensesFoodpreservativesTransparenttapeDisposable
diapersSportscarbodiesElectricblanketsCarbattery
casesSyntheticrubberVitamincapsulesRubbingalcoholIcecube
traysInsectrepellentRoofingshinglesShowercurtainsPlywood
adhesiveBeachumbrellasFaucet
washersAntihistaminesDrinkingcupsPetroleumjellyTennis
racketsWireinsulationBallpointpensArtificialturfArtificial
limbsShavingcream

Paint
brushesTelephonesInsecticidesAntisepticsFishing
luresDeodorantLinoleumSweatersPaint
rollersFloor waxPlastic woodModel carsTrash
bagsSoap dishesHand
lotionClotheslineShampooPanty hoseFishing
rodsOil filtersAnestheticsUpholsteryTV
cabinetsCassettesSalad bowlsHouse
paintAwningsAmmoniaSafety glassHair
curlersVCR tapesEyeglassesMovie filmIce
chestsLoudspeakersIce bucketsCredit
cardsFertilizersWater pipesToilet seatsFishing
bootsLife jacketsGarden hoseGolf
ballsUmbrellasDetergentsRubber cementSun
glassesCold creamBandagesHair coloringNail
polishGuitar stringsFalse teethToothpasteGolf
bagsToothbrushesPerfumeFolding doorsShoe
polishShower doorsCortisoneHeart valvesLP

Oil and The Environment

Air
Water
Land

Air
Preserving air quality around a refinery
involves controlling the following
emissions:

sulphur oxides
hydrocarbon vapours
smoke
smells

Water
The

majority of the water discharged

from the refinery has been used for
cooling the various process streams.
The cooling water does not actually
come into contact with the process
material and so has very little
contamination.

 Rainwater

falling on the refinery site

must be treated before discharge to
ensure no oily material washed off
process equipment leaves the refinery.
Process water has actually come into
contact with the process streams and
so can contain significant
contamination.

Land
The

refinery safeguards the land

environment by ensuring the appropriate
disposal of all wastes.
Within the refinery, all hydrocarbon wastes
are recycled through the refinery slops
system. This system consists of a network of
collection pipes and a series of dewatering
tanks. The recovered hydrocarbon is
reprocessed through the distillation units.