Introduction to Refining

Processes
Refining Processes:
1. Separation Processes
- Distillation
- Solvent deasphalting
- Solvent extraction
- Solvent dewaxing
2. Conversion processes
Thermal processes Catalytic processes:
- Thermal cracking - Catalytic Reforming
- Delayed coking - Catalytic cracking
- Visbreaking - Catalytic hydrocracking
- Headrotreatment
- Isomerization
- alkylation
- Catalytic polymerization
Petroleum Products:
1. liquefied Petroleum Gas (LPG)
2. Gasoline
3. Kerosene
4. Jet Fuel
5. Diesel Fuel
6. Fuel Oil
7. Residual Fuel Oil
8. lube Oil
9. Asphalt
10. Petroleum coke
INTRODUCTION TO
CRUDE OIL
DISTILLATION
 INTRODUCTION
 Petroleum is a mixture of liquid hydrocarbons having boiling
points ranging from - 100F to 1400.
 As a mixture, petroleum is little practical use. However, if we
separate various components from the crude, we are able to obtain
useful and saleable products. Examples of these components are
gasoline, aviation turbine kerosene, fuel oil, asphalt, and so forth.
 The process used in a refinery to carry out this separation is called
distillation.
 Distillation: is the process in which the components of a liquid
mixture are separated by boiling followed by re-condensation and
collection.
 Each component of a mixture has a particular boiling point so that
as the mixture is heated and its temperature rises, first one
component and then another boils off. In a hydrocarbon mixture, the
components with the lightest molecules have the lowest boiling
points.
 Distillation : The first step in the refining of crude oil, whether in a
simple or a complex refinery, is the separation of the crude oil into
fractions (fractionation or distillation).
 These fractions are mixtures containing hydrocarbon compounds
whose boiling points lie within a specified range.
 A continuous flow of crude oil passes from the storage tanks
through a heating coil inside a furnace, where it is heated to a
predetermined temperature.
 The heated oil then enters the fractionating column, which is a tall
cylindrical tower containing trays suitably spaced and fitted with
vapour inlets and liquid outlets (Figures 2 and 3).
 When two species A and B (A more volatile than B) are fed into the
distillation column and heated partial vaporization occurs.
 The vapor, richer in A, rises from the feed tray (tray 3) through the
bubble caps, bubbling through the liquid on tray 4, setting up a
vapor/liquid equilibrium. Tray 4 is cooler than tray 3, so some of
component B will condense, leaving the vapour rising from tray 4
richer in A.
 The same process is repeated on tray 5, and we are left with a vapour
leaving tray 5 very much richer in component A than was the original
feed.
 To keep a temperature differential between the trays, the top vapour
leaving tray 5 is condensed by cooling it, and some is fed back to the
top of the column, the remainder leaving as the top product.
 The liquid portion of the feed entering the column falls from tray 3 to
tray 2, which is hotter than the feed tray 3. On tray 2, because of the
increase in temperature, the vapour is richer in A than the liquid, so the
composition of the liquid on tray 2 is richer in component B than the
original feed. This liquid falls to tray 1, where the process is repeated.
 To ensure that the temperature falls from tray to tray going up the
column, some of the bottom product (rich in B) is heated and fed
back to the bottom tray. The remainder leaves as bottom product
rich in B.
 Thus, by the use of cooled top product (reflux) and heated bottom
product (reboil) the temperature difference between trays is
maintained, and fractional distillation occurs.
 It can also be seen that liquid drawn from any of the trays will
contain varying concentrations of A and B, changing from a mixture
rich in B at the bottom tray, to a mixture rich in A at the top tray.
 In distilling petroleum we are considering not just 2 components,
but many components.
 However, the same principles apply and by feeding heated oil to a
fractional distillation column, we can, by withdrawing liquid from
various trays, separate the oil into vary in fractions.
Main Components of Distillation Columns:
A vertical shell where separation
of liquid components is done.
•Column internals e.g.
trays/plates and/or packings
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.
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 vapour 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
• Vapour 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 vapour and liquid within the
column as well as external flows of feeds and product streams,
into and out of the column.
 Crude Oil Distillation Curves
 Types of distillation curves:
 1. TBP (True Boiling Point) distillation curve:
The true boiling point curve is basically a plot of the boiling point
of each component of the mixture as a function of the cumulative
volumetric fraction distilled. It implies that a batch distillation
column with a large number of trays and a large reflux ratio is used,
It consists of using a 15 to 18 tray distillation column operating at a
5:1 reflux ratio. The distilled volume is measured and the
temperature in the reboiler is recorded.
Cut point:
A cut point is defined as that temperature on the whole crude TBP
curve that represents the limits (upper and lower) of a fraction to be
produced. Consider the curve shown following Figure:
2. ASTM (D86/D1160) distillation curve:
 In practice, obtaining the TBP curves are time consuming and
expensive. other quicker methods have been developed. One such
method, used for almost all petroleum fractions, except for heavy
fractions, is the ASTM D86 method.
 In this test, the sample is boiled and the vapors are condensed and
collected as they are produced. Vapor temperatures are then
recorded as a function of cumulative liquid volume collected.
Because no reflux is used and there is only one equilibrium stage,
the initial boiling point of this assay is larger and the final point is
lower than the one in the TBP curve.
 Another distillation method used for heavy fractions is the ASTM
D1160. There is need to use this other method because
hydrocarbons start to crack at temperatures higher than about
340 oC. The ASTM D1160 is conducted at vacuum conditions (1 to
50 mmHg).
TBP/ASTM distillation curves: are the most important
characterization properties of the crude/intermediate/product
streams.
 Both TBP, ASTM distillation curves are measured at 1 atm
pressure.
 In both these cases, the boiling points of various volume
fractions are being measured.
 The basic difference between TBP curve and ASTM distillation
curve is that while TBP curve is measured using batch
distillation apparatus consisting of no less than 15 trays and very
high reflux ratio, the ASTM distillation is measured in a single
stage apparatus without any reflux.
3. The Equilibrium Flash vaporization (EFV) method:
 Consists of heating up a sample keeping vapor and liquid together
in the same vessel, that is, not separating it from the liquid phase
while it is produced, as in the other ASTM D86 and D1160
methods.
 The temperature is recorded as a function of the percentage
vaporized.
 Separation is poorer than in ASTM methods, and therefore, the
initial point is higher and the final point lower.
We illustrate the differences between these curves in the following
Figure :
 The methods of distillation

 There are three types of distillation processes have been used to

separate fractions within liquid mixtures.:
 Batch distillation ,
 Continuous distillation
 Fractional distillation.
 The major process used today is fractional distillation, with very
little use being made of either the batch or continuous distillation
processes.
 However, as fractional distillation is nothing more than an
extension or modernization of the older two processes.
 Batch Distillation
 In this operation, a set feed charge was made to the heater. The
temperature of the feed was then raised step by step.
 The overhead products obtained during each step rise in temperature
were then separated.
 When the contents of the feed vessel were heated to the maximum
desired temperature, the remainder of the feed charge (bottoms)
were pumped out, and the still allowed to cool .
 Continuous Distillation

 This operation, consisted of nothing more than a number of stills

hooked in series.
 Fresh feed was fed continuously to the first still. The temperature
of the first still was held lowest, the temperature on the second still
a little higher, and so forth.
 Fractional Distillation
 Fractional distillation is carried out in a tower with a number of side
streams in addition to the overhead receiver at the top and the
residuum outlet at the bottom. Each side-stream allows a condensate
with a particular boiling range to be removed from the tower.
 The more volatile components must rise to near the top of the tower
before the temperature is low enough to allow them to condense.
 The less volatile hardly evaporate at all and so fall from the inlet
point as liquids to leave the bottom.
Feed charge system of atmospheric distillation

 The atmospheric distillation unit is classified into the following

four types in terms of feed charge system as the following:
 Non-preflash system
 Preflash drum system
 Prefractionator system
 Dual flash system
 Non-preflash system
 Crude oil is sent directly to the atmospheric tower without being
processed by any preliminary separation equipment such as a
flash drum or a fractionation tower.
 Although this system is simple.
 Pressure drop through the crude oil furnace is high, occur due to
vaporization at the inlet of the furnace.

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 Preflash drum system
 The desalted crude oil is heated, and then introduced to a preflash
drum where flashed water and light hydrocarbons are separated.
 The flashed vapor is sent directly to the atmospheric tower.
 The flashed liquid is further heated by heat exchangers and a
crude oil furnace.
 This system reduces pressure drop through the crude oil furnace.

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 Prefractionator system
 A pre-fractionator is installed to remove gas and a part of the
naphtha fraction from the crude oil. Since gas and part of the
naphtha are removed in the pre-fractionator.
 The diameter of the atmospheric tower can be reduced.
 The pressure drop through the feed furnace may also be reduced.
 This system is often applied when processing crude oils that are
rich in gas and naphtha fractions.
 It is also applied as
a means of increasing
the capacity of an existing
unit.

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 Dual flash system
This system is applied to process two or more kinds of crude oil
whose properties (sulphur content of residue, for example) are very
different. An additional crude feed train (s) provided with flash
drum(s) is installed to yield separately the residue from each crude.

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 The fractionator overhead
(Reflux) system
 Reflux system classify to two types :
 Pump-around reflux system
 Overhead reflux system
 Reflux: liquid returned to top of the tower from the overhead
system.
 Pumparound: liquid is taken from the tower , cooled and returned
to the tower at a higher point.
 Overhead reflux system: in this system overhead vapour is
condensed by the overhead condenser and the condensed liquid
returns to the top of the atmospheric tower as a reflux.
 Overhead reflux system may be classified into:
 Cold reflux system
 Hot reflux system 29
 Pump-around reflux system
 This system alternatively called a side reflux system or a
circulating reflux system. A corresponds to this system , part of the
ascending vapor to the top section of atmospheric tower is
condensed on the top section trays by contacting the cooled pump-
around reflux liquid , and the condensed liquid flows down as
internal reflux. The heat load of the top pump-around reflux is
effectively utilized to heat the feed crude oil .
 Due to the large amount of pump-around reflux liquid, the diameter
of the tower top is comparatively large.
 pump-around : this corresponds with introducing some condensation
of the vapor at the top of intermediate columns.
 The trays between the liquid draw and return in a pumparound have
more to do with heat transfer than mass transfer.
 In addition to returning a sub cooled liquid to the column, mixing
occurs as material is introduced to a higher point in the column
Pump-around reflux system

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 Cold reflux system

The overhead vapor is condensed by an overhead condenser and

enters an accumulator (overhead reflux drum) where hydrocarbons
liquid , gases and water are separated. Part of the hydrocarbon liquid
is withdrawn from the drum as naphtha product. The remaining
hydrocarbon liquid is returned to the top of atmospheric tower . This
system is simple in operation. The diameter of the tower top section
is small and trays for the heat transfer are not required.

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 Hot reflux system

• Tow sets of overhead condensers and drums are arranged in series

in this system.
• A heavy fraction in the overhead vapor is condensed in the first
condenser and send to the first drum. All hydrocarbons liquid
accumulated in this drum is returned to the top of the atmospheric
tower as the reflux. The flashed hydrocarbons vapor and steam
from the first drum is then condensed in the second condenser, the
condensed hydrocarbons liquid withdrawn as a naphtha product.
Since the temperature of the reflux liquid is higher than that of cold
reflux system, this system is called a hot reflux system. the same
dimensional advantage mentioned for the cold reflux system is
expected. This system is complex in operation due additional
equipment and operating variables. .
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