Petroleum Refining Processes

Chem. Engr. Lina Fouzi Abdul Jawad

1
 Petroleum Refining
Processes 1
• Crude Oil Processing.
• Degassing and Dehydration-Desalting
• Atmospheric Distillation.
• Vacuum Distillation.

2
Crude Oil Processing
• The physical and chemical transformations
that crude oil undergoes in a refinery take
place in numerous distinct processes, each
carried out in a discrete facility, or process
unit.
• Large modern refineries comprise as many
as fifty distinct processes, operating in close
interaction.
• However, these processes can be thought of
in terms of a few broad classes, shown in the
following table 1. 3
Table 1. Important Classes of Refining Processes

4
Degassing and Dehydration-Desalting
• In a producing oilfield the fluid obtained at
the wellhead is submitted to degassing and
dehydration operations .
• In the first operation the gases evolved by
releasing the pressure of the fluid are
recovered, stripped of the less volatile
components, and either sent to consumer
centers as natural gas or used to repressurise
the oilfield.
• The stripped liquid components are
marketed as stabilized natural gasoline.
5
Figure 1. Crude Oil Degassing Station

6
 Dehydration and desalting of crude
• The second operation aims to completely eliminate the
water that appears in the fluid forming stable
emulsions, and the removal of water-soluble inorganic
salts associated with the water which, if left in the oil,
would give rise to serious corrosion problems in the
course of refining operation.
• All crude contain moisture and salts to varying degrees.
• Water is likely to occur in emulsion form when the
crude are naphthenic or sulfurous.
• No harm may be expected to the distillation column
due to the presence of moisture, as there is always
steam in distillation.
• However, crude has to be dehydrated to remove the
salts.
7
• Water being good solvent for these salts the removal
is very much effective in the form of brine.
• Of all of the existing salts, chlorides of calcium and
magnesium distinguish themselves in playing an
invincible role in overhead corrosion.
• These salts in presence of steam at 150-200 ◦C easily
hydrolyze generating hydrochloric vapors.
• These vapors cause corrosion to equipment.
• Any crude that contains more than 5 kg of total salts
expressed in terms of sodium chloride per thousand
barrels may be regarded as salty crude.
• Dehydration of crude is practiced in two stages, first
in the site and later in the refinery.
8
• At the site (oil field), salt is removed by:
1) settling
or by 2) adding chemicals
or by 3) Combination of these two.
• Crude possessing emulsifying
characteristics are not responsive to settling
method; these demand demulsifying agent
to increase the coalescence of water drops.
• Soda ash, sodium hydroxide, and salt of
fatty acids petroleum sulphonates which
assist coalescence of water droplets.
9
• A good amount of water should be available
in crude for such treatment; lack of water
demands the fresh additions to about 20 %.
• After adding the chemicals and water to the
desired extent the crude mixture is allowed
to stand 75-80 ◦C at 15 kg/cm2 in huge tall
tanks.
• Demulsifying chemicals, if necessary are
added in very small amounts.
• Retention time is about 48 hours.
10
Coalescence
• Water droplets will settle at a velocity proportional to the
square of their diameter
• Salt water is present in oil in the form of an emulsion,
created by dispersion of water in droplet form, and held
by emulsifying agents present in the oil.
• These emulsifying agent are generally:
Resin
Asphalts
Organic acids
Solids which are produced with the oil, and aid in the
formation of a tough film around the droplet, thus
isolating each separate water droplet from the other.
11
• The film which isolates the water droplets from
the other must be broken before coalescence take
place

1) Chemical aids are used to

de-emulsifiers displace this film
2) Heat from the water
droplet.
The proper use
of heat is also an
aid.
12
• The final phase of the coalescence
process is the collision of these
small water droplets under the
influence
3) An to form layer
electrostatic field drops which will
settle faster

13
Crude Oil Desalting
• Crude oils delivered to the refinery frequently
contain substantial quantities of water, silts, sand,
extraneous salts, etc.
• ‘‘Desalting’’ involves removal of most of these
impurities before further processing.
• If not removed they can increase scaling rates
(buildup of deposits) or cause blockages of
refinery equipment, such as heat exchangers, and
increase corrosion.
• Two desalting methods are in common use, each
using several processing units operating in series.
14
• Chemical desalting is accomplished by addition
of about 10% water to the oil to be treated, plus
sulfuric acid or sodium hydroxide as necessary
for crude pH adjustment.
• Reagents are added just before the oil enters the
desalting system charging pump to obtain good
mixing.
• The acid or base addition may be sufficient by
itself to cause rapid de- emulsification after
mixing, or a small concentration of a proprietary
de-emulsifier, such as Tretolite (a
polyethylenimine) may have to be added with the
water to assist the process.
15
Figure 2. Flow sheet for the main steps
involved in chemical de-salting.

16
• The mixture is then heated to 65-180
(depending on oil viscosity and boiling
point) and mixing is assured by passage
through a mixing valve.
• It is then held for a time to allow separation
of the oil and aqueous phases.
• Cleaned oil is drawn from the top of the
vessel and the aqueous phase containing the
salts, sand, silt, and other extraneous
material is drawn from the bottom.
17
• Electrostatic desalting is also common.
• As in chemical desalting, water is added to the oil
stream (to dissolve any suspended salts) and the
stream passed through a mixing valve into the de-
salter.
• Here oil-water separation is mainly accomplished
with a high-potential electrostatic field instead of
with demulsifying chemicals.
• The electrostatic field induces rapid coalescence
and settling of water droplets together with any
other water-associated impurities and ‘‘creaming’’
of the oil phase.
18
• The water phase is drawn continuously from the bottom
of the de-salter vessel and passed to the refinery effluent-
treatment plant.
• The oil phase is skimmed from the top for further
processing.
• Desalting by one or the other or both of these two
procedures is now a routine for the refining of most
crudes.
• It is also sometimes used as a secondary clean-up to
remove excess salt still remaining in distilled
atmospheric gas oil before it is further processed.
• Desalting techniques have recently been extensively
reexamined experimentally.

19
Crude Oil Distillation
• Distillation of crude oil accomplishes a rough sorting of
the main components on the basis of boiling point
differences.
• This was originally carried out on a batch basis, where
the crude oil to be distilled was entirely in place in the
distilling vessel at the start of heating.
• With a batch still the components of the crude are
obtained in vapor form in sequence as the heat is applied,
the lighter (lower boiling point) components first.
• Midrange and heavier, less volatile constituents are
distilled later in the sequence, eventually leaving behind
a viscous, high boiling point asphaltic residue in the
distilling vessel.
20
• Batch distillations are inefficient because of the need for
separate steps for filling, heating, stopping, pumping out
the residue, and refilling of the distilling vessel again.
• For this reason, they tend to be economic only for
distillations on a scale of less than 300 bbl/day (ca.
12,000 U.S. gallons, 10,000 Imp. gallons, or 45 m3 /day).
• This scale of production was only appropriate for local,
very small distillate requirements from a simple refinery,
which also happened to be close to a petroleum
producing area, not a common situation today.
• Even a small modern refinery distills 2,000-10,000
bbl/day and the largest American refineries process
175,000 bbl (27,800 m3) or more crude oil per day.

21
• These are all scales, which require continuous
operation for efficient production.
• For continuous distillation the crude oil is first
heated to 400-550while it is continuously
flowing through a pipe still, using natural gas,
‘‘light ends’’ (miscellaneous low boiling point
hydrocarbons), or fuel oil for fuel.
• The heated crude is then passed into a
fractionating tower near the bottom, the hotter
end of the tower.

22
• In the fractionating tower, a unit 2 - 3 m in
diameter and 30 - 40 m high for a large modern
refinery, the lower boiling components move up
as vapors.
• As the vapor moves upward past each plate of the
column it is forced, via the bubble caps (‘‘bell
caps’’) of that level, to pass through and come to
thermal equilibrium with the liquid on that plate
or tray.
• Hydrocarbons having a boiling point lower than
the temperature of the liquid on the plate will
continue to move up the column, in vapor form.
23
Partial cut-away
view of
continuous
crude oil
distillation via a
pipe still and
fractionating
column.
Frequently the
heat content of
the distillate
fractions is
employed to
preheat the
incoming crude
oil (not shown
here).
24
• Components of the heated crude having a boiling
point higher or the same as the temperature of the
liquid on the plate will tend to condense in the
liquid on the plate.
• As liquids of similar boiling points accumulate on
the plate they either overflow into the projecting
end of a downcomer pipe to the next lower plate,
or they are drawn off the plate and the column as
one of the product streams of the crude
distillation.
• The lower end of each downcomer is of sufficient
length that it dips some distance into the liquid on
the lower tray to prevent vapor movement up the
downcomer. 25
• In this way propane and butane (C3 and C4
hydrocarbons) that are the lowest boiling
components, and frequently some water, are
collected as vapors from the top of the fractionating
column.
• The vapors pass through a dephlegmator (a partial
condenser), which condenses naphtha, gasoline, and
water vapor components out of this vapor stream,
and allows passage of butane and lighter fractions
through as vapors (Table 2).
• Water is phase-separated from the condensed liquids
for removal in a unit outside the fractionating
column, and most of the condensed
naphtha/gasoline fraction is withdrawn from this as
a product stream. 26
• A part of the phase-separated hydrocarbon stream is
returned to the top plate of the fractionating column
as a reflux for temperature control.
• This return of condensed light distillate to a top
plate of the column is what controls the temperature
of the cool end of the fractionating column to
achieve the thermal gradient of 12-15/m required.
• The bottom and hot end of the column is kept at
about 500 via heat brought in through the entry of
preheated crude oil, already mostly vaporized, and
also occasionally by means of a reboiler operating at
the bottom of the column indirectly heated by heat
exchange fluid.
27
 Table 2. Atmospheric Pressure Boiling Point
Ranges, Trends in Properties, and Approximate
Composition of Representative Fractions from
Crude Oil Distillation

28
• To decrease the thermal gradient per meter of
height and sharpen (narrow) the boiling range of
each fraction separated from crude oil, the
fractionating column will occasionally be split into
two columns.
• One of these will normally operate over the
temperature range of about 40 to a maximum of
about 350-370 .
• The other will be used to fractionate all components
boiling above about 370 .
• This will normally operate under reduced pressure
to provide sharper fractions of the higher boiling
constituents of the crude, not possible with a single
column.
29
• Whether the crude distillation is conducted in
single or dual columns, the principle of
operation is the same.
• Hydrocarbon vapors plus a naphtha/gasoline
fraction boiling in the 40-180 range are the top
take-off products of the crude still.
• A kerosene/jet fuel fraction boiling at
approximately 180-230 is taken off a plate
further down the column, followed by fractions
of light gas oil, b.p. 230-300 , and heavy gas oil,
b.p. 300-400 , from the appropriate lower plates
of the column.
30
• The highest boiling distillate (i.e., volatile)
fraction from the crude still is the lubricating oil
stream, b.p. 400-520 , which also contains much
of the grease and wax yield of the crude oil.
• The residue or the bottom stream of the crude
fractionating tower includes all the crude
components not vaporized below about 520 , and
consists of mostly asphalt and suspended
petroleum coke.
• This is the highest distillation temperature
normally used for crude distillation because at
these temperatures the residual large hydrocarbon
constituents begin to decompose or break down.
31
• Since the boiling point ranges of the petroleum
cuts (fractions) obtained from the crude
distillation column(s) are quite wide, many of
these crude streams will be redistilled and/or
stripped to sharpen (narrow down) the boiling
point ranges.
• The gas stream that is composed of components
boiling below 40, is normally redistilled under
pressure.
• Pressure distillation increases the boiling point
and condensation temperatures of the components
present, which sharpens the separations and
enables condensation of many of the separated
compounds as liquids. 32
• At atmospheric pressure refrigeration would be
required to achieve condensation of these
components.
• A separate column is generally used for the final
clean-up of each of these components.
• The naphtha/gasoline, kerosene, and higher boiling
streams will usually be sharpened to narrower
boiling ranges than obtained directly from the
crude still by heating with steam in a reboiler to
strip (remove by vaporization) the excess volatiles.
• Alternatively, these streams may be redistilled in
small columns to separate each of them into two or
three separate sharper fractions.
33
• The trends in density, viscosity, sulfur content,
etc., that are obtained as one proceeds from the
low to higher boiling point fractions are quite
informative as to content (Table 2).
• For instance, as the carbon to hydrogen ratio
increases there is a corresponding increase in
density.
• Viscosity also increases steadily with an increase
in molecular size.
• The sulfur also tends to occur in the larger
molecules from the increase in sulfur content
observed with an increase in boiling point.
34
• The content of transition metals, such as
vanadium, nickel, and iron tends to predominate
with the high boiling and residual fractions of
crude oil distillation.
• Up to 250 ppm of vanadium is not uncommon in
the residues.
• Simple distillation, secondary distillation, and
stripping processes separate crude petroleum into
useful hydrocarbon fractions of similar physical
properties.
• Each fraction can contain from 5 to over 100
different compounds (Tables 2 and 3).
35
• But the proportions of the main fractions
separated vary widely depending on the origin of
the crude oil.
• Some crude oils contain as little as 1-2% of a
gasoline fraction.
• The demand for gasoline in Japan and Western
Europe is 16-20% of the petroleum refined, and
in the U.S., it is about double these figures (Table
4).
• In northern countries there is also a seasonal
swing in gasoline demand from 27% of refinery
output in winter to about 35% in summer.
36
• These poor matches between the
proportions of constituents actually
present in crude oil and the proportions
demanded of refineries means that
molecular modification of the crude
distillation fractions is necessary to
achieve a better correspondence of
product to demand.

37
Table 3. Some Primary and Secondary Uses of
the Gas Stream from Petroleum Refining

38
Table 4. Principal Uses and Demand Distribution
for the Primary LIQUID refinery Products

39
 Figure 3.
Fractionation
Towers

40
Fractionation Towers
• After desalting, the crude oil is pumped through a series
of heat exchanger and its temperature raised to about 550
o
F (288 oC ) by heat exchange with product and reflux
streams.
• It is then further heated to about 750 oF (399 oC ) in a
furnace (i.e. direct fired heater or "pipe still" ) and
charged to flash zone of atmospheric fractionators.
• The furnace discharge temperature is sufficiently high to
cause vaporization of all products with drawn above the
flash zone + about 20% of the bottom product.
• The 20 % "over flash" allows some fractionation to occur
on the trays just above the flashing zone by providing
internal reflux in excess of side stream withdrawals.
41
• In many petroleum distillations, steam is admitted
to the space in which vaporization occurs, the
steam reduce the partial pressure in the vapor by
Dalton's law, the boiling point of a material may
be reduced in only two ways:
• 1) the pressure may be reduced
• 2) or some inert gas such as steam may be introduced.
• The distillation causes the fractions to separate in
increasing order of boiling point.
• The top product being highly volatile has to be
condensed in a reflux condenser.
• Some portion of the condensed fraction goes back
as reflux.
42
• All other fractions form the side draw
products of distillation column.
• There fractions are usually classified as
heavy naphtha, kerosene, gas oil.
• Bottom product of atmospheric column is
now again routed through a furnace to reach
a temperature of 350 to 400 oC and is
allowed to flash in a vacuum column,
vacuum gas oil, heavy diesel, lubrications
oil cuts / pressure distillates shall be the side
cuts.
43
Figure 4.

44
Atmospheric Distillation
• Crude oil distillation is the front end of every
refinery, regardless of size or overall
configuration.
• It has a unique function that affects all the
refining processes downstream of it.
• Crude distillation separates raw crude oil feed
(usually a mixture of crude oils) into a number of
intermediate refinery streams (known as “crude
fractions” or “cuts”), characterized by their
boiling ranges (a measure of their volatility, or
propensity to evaporate).
45
• Each fraction leaving the crude distillation unit
• (1) is defined by a unique boiling point
range (e.g., 180oF – 250oF)
• and (2) is made up of hundreds or thousands
of distinct hydrocarbon compounds, all of
which have boiling points within the cut
range.
• These fractions include (in order of increasing
boiling range) light gases, naphthas, distillates,
gas oils and residual oil.
• Each goes to a different refinery process for
further processing.
46
• The naphthas are gasoline boiling range
materials; they usually are sent to upgrading units
(for octane improvement, sulfur control, etc.) and
then to gasoline blending.
• The distillates, including kerosene, usually
undergo further treatment and then are blended to
jet fuel, diesel and home heating oil.
• The gas oils go to conversion units, where they
are broken down into lighter (gasoline, distillate)
streams.
• Finally, the residual oil (or bottoms) is routed to
other conversion units or blended to heavy
industrial fuel and/or asphalt. 47
• The bottoms have relatively little economic
value - indeed lower value than the crude oil
from which they come.
• Most modern refineries convert, or upgrade,
the low-value heavy ends into more valuable
light products (gasoline, jet fuel, diesel fuel,
etc.).
• Because all crude oil charged to the refinery
goes through crude distillation, refinery
capacity is typically expressed in terms of
crude oil distillation throughput capacity.
48
Vacuum
Distillation

49
Vacuum distillation
• Vacuum distillation is distillation performed under
reduced pressure, which allows the purification of
compounds not readily distilled at ambient pressures or
simply to save time or energy.
• This technique separates compounds based on
differences in boiling points.
• This technique is used when the boiling point of the
desired compound is difficult to achieve or will cause
the compound to decompose.
• A reduced pressure decreases the boiling point of
compounds.

50
Vacuum distillation in petroleum refining
• Petroleum crude oil is a complex mixture of
hundreds of different hydrocarbon compounds
generally having from 3 to
60 carbon atoms per molecule, although there
may be small amounts of hydrocarbons outside
that range.
• The refining of crude oil begins with distilling
the incoming crude oil in a so-
called atmospheric distillation
column operating at pressures slightly above
atmospheric pressure.
51
• Vacuum distillation can also be referred to as
"low-temperature distillation".
• In distilling the crude oil, it is important not to
subject the crude oil to temperatures above 370
to 380 °C because high molecular
weight components in the crude oil will
undergo thermal cracking and form petroleum
coke at temperatures above that.
• Formation of coke would result in plugging the
tubes in the furnace that heats the feed stream to
the crude oil distillation column.

52
• Plugging would also occur in
the piping from the furnace to the
distillation column as well as in the column
itself.
• The constraint imposed by limiting the
column inlet crude oil to a temperature of
less than 370 to 380 °C yields a residual oil
from the bottom of the atmospheric
distillation column consisting entirely of
hydrocarbons that boil above 370 to 380 °C.

53
• To further distill the residual oil from the
atmospheric distillation column, the distillation
must be performed at absolute pressures as low
as 10 to 40 mmHg / Torr (About 5% atmospheric
pressure) so as to limit the operating
temperature to less than 370 to 380 °C.
• Figure 2 is a simplified process diagram of a
petroleum refinery vacuum distillation column
that depicts the internals of the column and
Figure 3 is a photograph of a large vacuum
distillation column in a petroleum refinery.

54
• The 10 to 40 mmHg absolute pressure in a vacuum
distillation column increases the volume of vapor
formed per volume of liquid distilled.
• The result is that such columns have very large
diameters.
• Distillation columns such those in Images 1 and 2, may
have diameters of 15 meters or more, heights ranging up
to about 50 meters, and feed rates ranging up to about
25,400 cubic meters per day (160,000 barrels per day).
• The vacuum distillation column internals must provide
good vapor–liquid contacting while, at the same time,
maintaining a very low-pressure increase from the top of
the column top to the bottom.
55
• Therefore, the vacuum column uses distillation trays only
where withdrawing products from the side of the column.
• Most of the column uses packing material for the vapor–
liquid contacting because such packing has a lower
pressure drop than distillation trays.
• This packing material can be either structured sheet
metal or randomly dumped packing such as Raschig
rings.
• The absolute pressure of 10 to 40 mmHg in the vacuum
column is most often achieved by using multiple stages of
steam jet ejectors.
• Many industries, other than the petroleum refining
industry, use vacuum distillation on a much a smaller
scale.

56
 Figure 4.
Large-scale
vacuum
distillation
tower.

57
Atmospheric and Vacuum Distillation Units

• Distillation of crude oil is carried out in two units,

first in an Atmospheric Distillation Unit (also
known as Crude Distillation Unit, CDU), with
further processing of the residue from
atmospheric distillation in the Vacuum
Distillation Unit (VDU), as illustrated in Figure 6.
• For sake of simplicity, Figure 6 does not include
the network of heat exchangers and pump around
loops to pre-heat the desalted crude before it is
fed into the fired furnace.

58
• In the furnace, the crude is heated to the desired
temperatures (700-750° F) such that all the distillate
fraction and roughly 10-20% of the bottom product are
evaporated, depending on the volatility of crude oil.
• The two-phase mixture is then introduced into the CDU
flash zone for separation of vapor and liquid streams
where vapor fraction rises toward the top of the column
and the liquid fraction is subjected to stripping with
steam to recover the low-boiling distillate components
dissolved in heavier liquid before sending the bottom
product (i.e., atmospheric distillation residue) to the
vacuum distillation unit.

59
Figure 5. Desalting by using gravity settling
to separate brine from crude oil.

60
Figure 6. An overall flow for fractional distillation of crude oil.

61
Schematic of an overall flow for fractional distillation.
• Crude oil enters a desalter and then a heater.
• It then undergoes an atmospheric distillation
where it refluxes.
• From that Heavy Gas Oil, Light Gas Oil,
Kerosene, Light. & Heavy Naphtha and LPG and
Fuel gas are separated out.
• The atmospheric residue goes to a separate heater
and then into a vacuum distillation right where
light vacuum gas oil and heavy vacuum gas oil
are separated out along with vacuum residue.
62
• A temperature gradient is established in the
column by removing heat from the overhead
vapor.
• The column condenses the naphtha fraction and
sends a portion of the liquid naphtha, as reflux, to
the column to achieve a good separation of the
distillate products drawn from the side of the
distillation column, such as kerosene, LGO, and
HGO, as seen in the diagram.
• Steam strippers on the side of the column also
provide reflux to the main column to help with
clean separation of the distillate products.
63
• Additional reflux is provided to the main column
by pump around loops associated with heat
exchangers.
• Counter-current flow of vapor and liquid streams
through the contact stages (e.g., trays) in the main
column, enabling good separation of the distillate
fractions.

64
• The temperature at the bottom of CDU is limited
to 700-750° F to prevent cracking - breaking of
the chemical bonds between carbon atoms in the
aliphatic hydrocarbons constituting the crude oil.
• Cracking would cause coking (accumulation of
carbonaceous solids) on the metal surfaces in the
column and interferes with fractionation in
distillation.
• Vacuum distillation is necessary to fractionate
the heavy distillates because further increase in
temperature would cause thermal cracking of the
feed components.
65
 Figure 7.
A schematic
diagram of
atmospheric
distillation
unit
illustrating
the feed heat
exchangers,
pump
around
loops, and
side steam
strippers.

66
• As shown in Figure 5, below, the atmospheric
residue is reheated in a fired furnace to 730-850°
F before introduction into the vacuum distillation
unit (VDU).
• The furnace outlet temperature is selected
depending on the thermal reactivity (or coking
propensity of crude oil) and the desired level of
separation in the column.
• Steam ejectors, or, more recently, vacuum
pumps, are used to create a vacuum for
evaporation of the light vacuum gas oil and
heavy vacuum gas oil fractions.
67
• The temperature and pressure in VDU also
depend on whether steam is introduced, or the
separation is carried out without the steam
addition in “dry” towers, varying between 10 to
30 mmHg at the bottom of the tower.
• Lower pressures and higher temperatures are
used in dry towers.
• To minimize the pressure difference between the
bottom and top of the column, some special
packing materials are used (see, for example,
Figure 9) instead of trays for providing contact
between liquid and vapor streams to improve
fractionation.
68
• The heavy distillates (light vacuum gas oil and
heavy vacuum gas oil) separated in VDU are
further processed in downstream separation and
conversion units to produce lubricating oil base
stocks, or as feedstock for hydrocracking to
produce light and middle distillates.
• The residue from vacuum distillation (VDR) can
be upgraded into marketable products and fuels
using processes such as visbreaking, de-
asphalting, and coking, as will be discussed in
later sections.

69
 Figure 8.
Vacuum
distillation
unit
and
processing
paths
for
vacuum
distillates.

70
Schematic of a vacuum distillation unit.
• Atmospheric residue enters a heater and then a vacuum
distillation tower.
• This tower has a pressure of 3 mmHg at the top and
28mgHG at the bottom.
• Steam is used to create the vacuuming in the tower.
• The flaring and sour water are products of steam production.
• The vacuum distillation tower yields heavy distillate which
can become lube oil base stocks or be sent to conversion
units (hydrocracking).
• Additionally, there is some vacuum residue which goes to
de-asphalting or coking.

71
 Figure 9.
Examples
of
packing
materials
to
achieve
low-pressure
drop
in
vacuum
distillation
columns.

72
Thank you

73