OIL REFINERY PROCESSES

Early Refining

1) By 1860 there were 15 refineries in operation.

2) Known as "tea kettle" stills, ( a large iron drum and a
long tube which acted as a condenser ).
Capacity ranged ( from 1 to 100 barrels a day.)
A coal fire heated the drum, and three fractions were
obtained during the distillation process. The first
component to boil off was the highly volatile naphtha.
Next came the kerosene, or "lamp oil", and lastly came
the heavy oils and tar which were simply left in the
bottom of the drum. These early refineries produced
about 75% kerosene, which could be sold for high profits.
 Early Refining
Later these waste streams were converted into valuable
products. In 1869 Robert Chesebrough discovered how
to make petroleum jelly and called his new product
Vaseline. The heavy components began being used as
lubricants, or as waxes in candles and chewing gum. Tar
was used as a roofing material. But the more volatile
components were still without much value. Limited
success came in using gasoline as a local anesthetic and
liquid petroleum gas (LPG) in a compression cycle to
make ice. The success in refined petroleum products
greatly spread the technique. By 1865 there were 194
refineries in operation.
 A Few Terms

Natural Gas is a mixture of very low boiling hydrocarbons. Natural gas can only be
liquefied under extremely high pressures and very low temperatures. It is called "dry"
when methane (CH4) is the primary component, and "wet" if it contains higher boiling
hydrocarbons. If it smells bad, because of sulfur compounds, it is called "sour". Otherwise,
it is called "sweet".
Liquefied Petroleum Gas (LPG) is a very light fraction of petroleum. It is also a fairly
simple fraction containing mainly propane and butane

Gasoline is a light fraction of petroleum which is quite volatile and burns rapidly. Straight
run gasoline refers to gasoline produced by distillation instead of cracking, although it
really doesn't make a difference. Gasoline is often just called "gas", however it is a liquid
at typical pressure

Naphtha is a light fraction of petroleum used to make gasoline. Naphtha also produces
solvents and feedstock for the petrochemical industry.
 A Few Terms

Kerosene was the first important petroleum fraction, replacing whale oils in lamps over a
hundred years ago. Some unscrupulous refiners failed to distill off all the naphtha from the
kerosene fraction thereby increasing the volume of their final product. This lead to many
lamp explosions and fires.

Diesel fuels find use in the fleet of trucks which transport the nations goods. Diesel
engines power these larger engines, and use higher compression ratios (and temperatures)
than their gasoline cousins. They are therefore more efficient. It is also interesting to note
that diesel engines have no spark plugs, instead the fuel-air mixture is ignited by the rising
temperatures and pressures during the compression stroke.

Gas Oil (or fuel oils) are used for domestic heating. In the winter refineries produce more
gas oil, whereas during the summer driving months they produce more gasoline.

Heavy Fuel Oil is often blended with gas oils for easier use in industry. Ships burn heavy
fuel oils but they call it bunker oil.
 A Few Terms

Atmospheric Residual is everything that cannot be vaporized under normal pressures.

Atmospheric residual is fed into another distillation column, operating at lower pressures,
which can separate out some of the lighter compounds. Lubricants and waxes reside in this
fraction.

Vacuum Residual is the bottom of the barrel. It includes asphalt and some coke.

Pitch is a thick, black, sticky material. It is left behind when the lighter components of coal
tar or petroleum are distilled off. Pitch is a "natural" form of asphalt.

Asphalt is a high boiling component of crude oil. It is therefore found at the "bottom of the
barrel" when petroleum is distilled.

Tars are byproducts formed when coke is made from coal or charcoal is made from wood.
It is a thick, complex, oily black mixture of heavy organic compounds very similar to pitch
or asphalt, though from a different source.
1. INTRODUCTION
INTRODUCTION
 Oil refining is a key activity in the CPI.
 Over 600 refineries worldwide have a total annual
capacity of more than 3500 x 106 tones.
 Goal of oil refining is twofold:
i. production of fuels for transportation, power generation
and heating; and
ii. production of raw materials for the CPI.
 Oil refineries are complex plants but are relatively
mature and highly integrated.
Crude Oil

Crude oil is a non-uniform material. The composition depends on its location.

The majority of crude oil is alkanes, cycloalkanes (naphthenes), aromatics,
polycyclic aromatics, S-containing compounds, etc.
Gasoline: branched alkanes
Diesel: linear alkanes
Heavier crude contains more polycyclic aromatics
Lead to carbonaceous deposits called “coke”
Some crudes contain a lot of sulfur, which leads to processing
considerations.
Refining operations & processes
 After desalting and dehydration, crude is separated
into fractions by distillation.
 The distilled fractions can not be used directly.
 The reason for such a complex set of processes is
the difference between the crude oil properties and
the needs of the market.
 Another reason for complexity is environmental.
Legislation demands cleaner products and is the
major drive for process improvement and
development of novel processes.
 Refining operations

Petroleum refining processes and operations can be separated

into five basic areas:
1. Fractionation (distillation) is the separation of crude oil in
atmospheric and vacuum distillation towers into groups of
hydrocarbon compounds of differing boiling-point ranges
called "fractions" or "cuts."
2. Conversion Processes change the size and/or structure of
hydrocarbon molecules. These processes include: :
 Decomposition (dividing) by thermal and catalytic cracking;
 Unification (combining) through alkylation and polymerization;
and
 Alteration (rearranging) with isomerization and catalytic
reforming.
Refining operations
3. Treatment Processes to prepare hydrocarbon
streams for additional processing and to prepare
finished products. Treatment may include removal or
separation of aromatics and naphthenic, impurities
and undesirable contaminants. Treatment may involve
chemical or physical separation e.g. dissolving,
absorption, or precipitation using a variety and
combination of processes including desalting, drying,
hydrodesulfurizing, solvent refining, sweetening,
solvent extraction, and solvent dewaxing.
Refining operations

4. Formulating and Blending is the process of mixing and

combining hydrocarbon fractions, additives, and other
components to produce finished products with specific
performance properties.
5. Other Refining Operations include:
 light-ends recovery;
 sour-water stripping;
 solid waste, process-water and wastewater treatment;
 cooling, storage and handling and product movement;
 hydrogen production;
 acid and tail-gas treatment;
 and sulfur recovery.
Refining operations

 Auxiliary Operations and Facilities include:

 light steam and power generation;
 process and fire water systems;
 flares and relief systems;
 furnaces and heaters;
 pumps and valves;
 supply of steam, air, nitrogen, and other plant gases;
 alarms and sensors;
 noise and pollution controls;
 sampling, testing, and inspecting and laboratory;
 control room;
 maintenance; and
 administrative facilities.
Flow scheme of a modern refinery
Desalting/dehydration
 Crude oil often contains water, inorganic salts, suspended solids, and
water-soluble trace metals.
 Step 1 in the refining process is to remove these contaminants so as
to reduce corrosion, plugging, and fouling of equipment and to prevent
poisoning catalysts in processing units.
 The two most typical methods of crude-oil desalting are chemical and
electrostatic separation, and both use hot water as the extraction
agent.
 In chemical desalting, water and chemical surfactant (demulsifiers) are
added to the crude, which is heated so that salts and other impurities
dissolve or attach to the water, then held in a tank to settle out.
 Electrical desalting is the application of high-voltage electrostatic
charges to concentrate suspended water globules in the bottom of the
settling tank. Surfactants are added only when the crude has a large
amount of suspended solids.
 A third (and rare) process filters hot crude using diatomaceous earth.
Desalting/dehydration

 The crude oil feedstock is heated to 65-180°C to reduce viscosity and

surface tension for easier mixing and separation of the water. The
temperature is limited by the vapor pressure of the crude-oil
feedstock.
 In both methods other chemicals may be added. Caustic or acid may
be added to adjust the pH of the water wash.
Desalting/dehydration
 Physical and chemical processes

Chemical
Physical
Thermal Catalytic
Distillation Visbreaking Hydro treating
Solvent extraction Delayed coking Catalytic reforming
Propane deasphalting Catalytic cracking
Solvent dewaxing Hydro cracking
Blending Catalytic dewaxing
Alkylation
Polymerization
Isomerization
2. PHYSICAL PROCESSES
How does distillation work?
 Distillation is defined as:
 a process in which a liquid or vapour mixture of two or
more substances is separated into its component fractions
of desired purity, by the application and removal of heat.
How does distillation work?

 Distillation is based on the fact that the vapour of a boiling

mixture will be richer in the components that have lower
boiling points.
 Thus, when this vapour is cooled and condensed, the
condensate will contain the more volatile components. At
the same time, the original mixture will contain more of
the less volatile components.
 Distillation is the most common separation technique and
it consumes enormous amounts of energy, both in terms
of cooling and heating requirements.
 Distillation can contribute to more than 50% of plant
operating costs.
How does distillation work?

Distillation columns are classified by the manner in

which they are operated:
1. Batch, in which the feed to the column is introduced
batch-wise. That is, the column is charged with a 'batch'
and then the distillation process is carried out. When the
desired task is achieved, a next batch of feed is
introduced.
2. Continuous columns process a continuous feed
stream. No interruptions occur unless there is a problem
with the column or surrounding process units. They are
capable of handling high throughputs and are the most
common of the two types.
Continuous distillation columns
Classified according to:
1. Nature of the feed that they are processing:
 binary column - feed contains only two components;
 multi-component column - feed contains more than two components.
2. Number of product streams they have:
 multi-product column - column has more than two product streams.
3. Where extra feed exits when used to help with the
separation:
 extractive distillation - where the extra feed appears in the bottom
product stream;
 azeotropic distillation - where the extra feed appears at the top
product stream.
4. Type of column internals:
 tray column - trays of various designs used to hold up the liquid to
provide better contact between vapor and liquid;
 packed column - packing are used to enhance vapor-liquid contact.
 Main Components of Distillation Columns

 A vertical shell where separation

of liquid components is done.
 Column internals e.g. trays/plates
and/or packing which are used to
enhance component separations.
 A reboiler to provide the
necessary vaporization for the
distillation process.
 A condenser to cool and
condense the vapor leaving the
top of the column.
 A reflux drum to hold the
condensed vapor from the top of
the column so that liquid (reflux)
can be recycled back to the
column.
Trays and plates

Bubble cap trays

A riser or chimney is fitted
over each hole, and a cap
covers the riser. The cap is
mounted with a space to
allow vapour to rise
through the chimney and
be directed downward by
the cap, finally discharging
through slots in the cap,
and bubbling through the
liquid on the tray.
Trays and plates

Valve trays
Perforations are covered by caps
lifted by vapour, which creates a
flow area and directs the vapour
horizontally into the liquid.

Sieve trays
Sieve trays are simply metal plates
with holes in them.Vapour passes
straight upward through the liquid
on the plate. The arrangement,
number and size of the holes are
design parameters.
Liquid and vapour flows in a tray column
Liquid and vapour flows in a tray column
 Each tray has 2 conduits called
downcomers: one on each side.
Liquid falls by gravity through the
downcomers from one tray to
the tray below.
 A weir ensures there is always
some liquid (holdup) on the tray
and is designed such that the the
holdup is at a suitable height, e.g.
such that the bubble caps are
covered by liquid.
 Vapour flows up the column and
is forced to pass through the
liquid via the openings on each
tray. The area allowed for the
passage of vapour on each tray is
called the active tray area.
 Packings
 Packings are passive devices designed to increase the interfacial area for
vapour-liquid contact.
 They do not cause excessive pressure-drop across a packed section,
which is important because a high pressure drop would mean that
more energy is required to drive the vapour up the distillation column.
 Packed columns are called continuous-contact columns while trayed
columns are called staged-contact columns because of the manner in
which vapour and liquid are contacted.
 Basic operation

 The feed is introduced somewhere near

the middle of the column to a tray
known as the feed tray.
 The feed tray divides the column into a
top (enriching or rectification) and a
bottom (stripping) section.
 The feed flows down the column where
it is collected in the reboiler.
 Heat (usually as steam) is supplied to the
reboiler to generate vapor.
 The vapor from the reboiler is re-
introduced into the unit at the bottom of
the column.
 The liquid removed from the reboiler is
known as the bottoms product or simply,
bottoms.
Basic operation

 Vapor moves up the column, exits the top, and is cooled in a

condenser. The condensed liquid is stored in a holding vessel known as
the reflux drum. Some of this liquid is recycled back to the top of the
column and this is called the reflux. The condensed liquid that is
removed from the system is known as the distillate or top product.
 Thus, there are internal flows of vapor and liquid within the column as
well as external flows of feeds and product streams, into and out of
the column.
Crude distillation
 Step 1 in the refining process is the separation of crude oil
into various fractions or straight-run cuts by distillation in
atmospheric and vacuum towers. The main fractions or
"cuts" obtained have specific boiling-point ranges and can
be classified in order of decreasing volatility into gases,
light distillates, middle distillates, gas oils, and residuum.
Atmospheric distillation
 The desalted crude feedstock is preheated using recovered
process heat. The feedstock then flows to a direct-fired
crude charge heater then into the vertical distillation
column just above the bottom, at pressures slightly above
atmospheric and at temperatures ranging from 340-370°C
(above these temperatures undesirable thermal cracking
may occur). All but the heaviest fractions flash into vapor.
Atmospheric distillation
As the hot vapor rises in the tower, its temperature is reduced. Heavy fuel oil
or asphalt residue is taken from the bottom. At successively higher points on
the tower, the various major products including lubricating oil, heating oil,
kerosene, gasoline, and uncondensed gases (which condense at lower
temperatures) are drawn off.
Simple crude distillation
Vacuum distillation

 To further distill the residue or topped crude from the

atmospheric tower without thermal cracking, reduced
pressure is required.
 The process takes place in one or more vacuum distillation
towers.
 The principles of vacuum distillation resemble those of
fractional distillation except that larger diameter columns
are used to maintain comparable vapor velocities at the
reduced pressures.
 A typical first-phase vacuum tower may produce gas oils,
lubricating-oil base stocks, and heavy residual for propane
deasphalting.
 A second-phase tower operating at lower vacuum may
distill surplus residuum from the atmospheric tower, which
is not used for lube-stock processing, and surplus residuum
Vacuum distillation
Modern crude distillation
Propane deasphalting

 Coke-forming tendencies of heavier distillation

products are reduced by removal of asphaltenic
materials by solvent extraction.
 Liquid propane is a good solvent (butane and
pentane are also commonly used).
 Deasphalting is based on solubility of
hydrocarbons in propane, i.e. the type of molecule
rather than RMM as in distillation.
Propane deasphalting
Solvent extraction and dewaxing

 Solvent treating is a widely used method of refining lubricating oils as

well as a host of other refinery stocks.
 Since distillation (fractionation) separates petroleum products into
groups only by their boiling-point ranges, impurities may remain. These
include organic compounds containing sulfur, nitrogen, and oxygen;
inorganic salts and dissolved metals; and soluble salts that were present
in the crude feedstock.
 In addition, kerosene and distillates may have trace amounts of
aromatics and naphthenes, and lubricating oil base-stocks may contain
wax.
 Solvent refining processes including solvent extraction and solvent
dewaxing usually remove these undesirables at intermediate refining
stages or just before sending the product to storage.
 Solvent extraction

 The purpose of solvent extraction is to prevent corrosion,

protect catalyst in subsequent processes, and improve finished
products by removing unsaturated, aromatic hydrocarbons
from lubricant and grease stocks.
 The solvent extraction process separates aromatics,
naphthenes, and impurities from the product stream by
dissolving or precipitation. The feedstock is first dried and
then treated using a continuous countercurrent solvent
treatment operation.
 The solvent is separated from the product stream by heating,
evaporation, or fractionation, and residual trace amounts are
subsequently removed from the raffinate by steam stripping or
vacuum flashing.
Aromatic solvent extraction unit
Furfural C5H4O2
 Solvent dewaxing
 Solvent dewaxing is used to remove wax from either distillate or residual
basestock at any stage in the refining process.
 There are several processes in use for solvent dewaxing, but all have the
same general steps, which are::
 mixing the feedstock with a solvent;
 precipitating the wax from the mixture by chilling; and
 recovering the solvent from the wax and dewaxed oil for recycling by
distillation and steam stripping.
 Usually two solvents are used: toluene, which dissolves the oil and
maintains fluidity at low temperatures, and methyl ethyl ketone (MEK),
which dissolves little wax at low temperatures and acts as a wax
precipitating agent.
 Other solvents sometimes used include benzene, methyl isobutyl ketone,
propane, petroleum naphtha, ethylene dichloride, methylene chloride, and
sulfur dioxide.
 In addition, there is a catalytic process used as an alternate to solvent
dewaxing.
Solvent dewaxing unit
Solvent dewaxing unit
 Blending

 Blending is the physical mixture of a number of different liquid

hydrocarbons to produce a finished product with certain desired
characteristics.
 Products can be blended in-line through a manifold system, or batch
blended in tanks and vessels.
 In-line blending of gasoline, distillates, jet fuel, and kerosene is
accomplished by injecting proportionate amounts of each component
into the main stream where turbulence promotes thorough mixing.
 Additives including octane enhancers, anti-oxidants, anti-knock agents,
gum and rust inhibitors, detergents, etc. are added during and/or after
blending to provide specific properties not inherent in hydrocarbons.
CHEMICAL PROCESSES
Thermal Catalytic
Visbreaking Hydro treating
Delayed coking Catalytic reforming
Catalytic cracking
Hydro cracking
Catalytic dewaxing
Alkylation
Polymerization
Isomerization
 Visbreaking

In Visbreaking operation, a mild thermal cracking is carried out. Visbreaking

produces Naphtha, Gasoil and a residue. The residue has lower viscosity
and pour point and hence can easily meet the requirements of the fuel oil
specifications in the fuel oil blending pool. Visbreaking basically breaks the
long paraffinic side chains attached to aromatic structures. Due to this the
residue pour point and viscosities are considerably reduced.
Two classes of reactions occur during visbreaking
 Cracking of side chained aromatic compounds to produce short chained
aromatics and paraffins
 Cracking of large molecules to form light hydrocarbons
Process Technology
Steps involved;
 Visbreaking is carried out either in a coil or in a soaker.
 When coil technology is used, the mild thermal cracking is carried out in
the furnace coils
 When soaker technology is adopted, the cracking is carried out in a soaker
unit that is kept immediately after the furnace.
 After cracking, the products are at high temperatures (480oC for coiled
furnace case or 430oC for the soaker)
 After cracking, the products are cooled using quenching operation.
 Quenching is a direct heat transfer mechanism in which a hot stream is
cooled with a hydrocarbon or water to reduce the temperature of the
system drastically.
 After quenching, the mixture is fed to a distillation column supplemented
with a side column and a partial condenser
 From partial condenser, water, naphtha and gas are produced. Naphtha
liquid stream is sent as a reflux for the column.
 The side column is fed with steam and produces gas oil. Steam enhances
hydrocarbon volatility as explained before in the lecture devoted towards
crude distillation process.
Coking
 Coking refers to extreme thermal cracking process
 Coking is a batch reaction. Feed is heated to 480 – 510oC and left for some
time so that coke and lighter products form.
 Since coking is a batch reaction, there can be different ways to carry out
coking.
 There are two types of refinery coking processes namely delayed coking
and fluid coking.
 Delayed coking: The heated feed is fed to a coke drum and coke forms in
the drum. The lighter products are withdrawn from the top section of the
delayed coker. After coking,the coke drum is full of coke and it is then
removed using water jets. The process is called delayed coking because in
this process the coal is heated using a much more complex system , and it
consists of multiple furnaces or coke drums. Usually the coal is heated at a
lower temperature for shorter periods of time , which removes water and
other by – products more slowly than the conventional process, thereby
increasing the overall time span.
Delayed Coking
 Fluid coking: The heated feed is fed to a fluidized bed where
coke particles with finer particle sizes would aid fluidization.
After coking, lighter products are withdrawn as overhead
vapour and coke thus formed is removed continuously. The
fluid coker also has an additional scrubber which will remove
heavier compounds from the vapors (if any) and send them
back with the feed stream. Here, the feed stream absorbs
heavier hydrocarbons from the vapors generated. This is
required as it is difficult to keep heavier hydrocarbons in the
feed phase only due to pertinent high temperatures. The coke
after coking reaction is cold coke. Therefore, to generate hot
coke, a burner unit is used to heat the coke using exothermic
CO2 reaction. The offgases from the burner are sent to
cyclones, scrubbing and then to the vent. The hot coke thus
obtained is recycled back to the fluidized bed or taken out as a
net coke product.
Fluid Coking
The coker products are fed to a complex distillation column i.e., main column
supplemented with side columns. From the complex distillation column,
naphtha, water, light gas oil and heavy gas oil are obtained.
 Additional complexities in the distillation unit are
 Feed entering the distillation column but not the coker unit: This is to
facilitate the removal of light ends from the feed (if any) and don’t subject
them to cracking. This is also due to the reason that light ends are valuable
commodities and we don’t want to loose them to produce cheap coke
product. In this case, the bottom product from the distillation column is fed
to the furnace for pre-heating and subsequent coking operation.
 Live steam in distillation: This is to facilitate easy removal of lighter
hydrocarbons in various sections.
 Circulatory reflux (Pump around units): This is to facilitate good amount of
liquid reflux in various sections of the main column. For Further details, of the
above two issues, please refer to the crude distillation lecture notes.