1.

ATMOSPHERIC DISTILLATION
Crude oil from the desalter is heated in a train of heat exchangers up to a temperature
of 250°C–260°C and further by a tube-still heater (also known as a pipe-still
furnace) to a temperature of 350°C–360°C. Hot crude is then flashed into a distillation
column, which is a tall, multiplated cylindrical vessel that separates the petroleum
fractions according to the differences in volatility. Top pressure is maintained
at 1.2–1.5 atm such that the distillation operation can be carried out at a pressure
close to atmospheric pressure and for this reason this column is also known as
the atmospheric distillation column. Vapours from the top of the column, consisting
of hydrocarbon gases and naphtha, emerge at a temperature of 120°C–130°C.
Part of this overhead liquid (oil phase only) is returned to the top plate of the column as overhead reflux
and the rest of the liquid is drawn and sent to a stabilizer column which separates
gases from liquid naphtha. A few plates below the top plate, the kerosene fraction
is drawn at a draw temperature of 190°C–200°C. A part of this fraction is returned
to the column after it is cooled by a heat exchanger.
The rest of the draw is passed to a side stripper where it is
cooled and sent to a storage tank as raw kerosene,
also known as straight run kerosene, which boils in the range of 140°C–270°C.
A few plates below the kerosene draw plate, the diesel fraction
is drawn at a temperature of
280°C–300°C. After cooling, part of this is returned to the column as circulating
reflux and the rest is steam stripped through a side stripper, like kerosene, to adjust
the flash point. This diesel fraction, with a boiling range of 270°C–340°C, from
the stripper is then cooled and sent to storage. In some refineries, jute batching
oil (JBO), which is an intermediate cut between diesel and the bottom residue, is
also drawn at a draw temperature of 300°C–330°C followed by steam stripping.
Residual oil drawn from the bottom of the column is known as reduced crude oil
(RCO). The temperature of the stream at the bottom
reaches around 340°C–350°C, well below the cracking temperature of oil. RCO is a brown to deep
chocolate-coloured stream containing high boiling fractions
that cannot be vaporised at the prevailing temperature and atmospheric pressure of
the column without cracking.

2. VACUUM DISTILLATION

vacuum distillation of the atmospheric residue

yields additional and valuable distillates, which could otherwise be thermally destroyed
if further distillation was attempted at atmospheric pressure and above.Hot RCO either from the steam-
heated storage
tank or from the bottom of the atmospheric distillation column is pumped through a
series of preheaters (heat exchanger train) followed by heating in a pipe-still heater to
raise the temperature to 360°C–370°C. This hot stream is then flashed in a multiplated
Distillation column where vacuum (below atmospheric pressure) is maintained by steam
Ejectors.
Usually, three ejectors are used; the first stage sends the uncondensed vapour to the second stage
followed by condensation. The uncondensed vapour then enters the third stage followed by
condensation and the uncondensed vapour from the third stage is vented out through
a flare or stack. A vacuum of 30–40 mm of mercury is maintained at the top of the column
and 100–120 mm at the bottom. Condensates from these ejectors are collected in
a drum, known as a hot well. The oily layer is then sent to an oil–water separator vessel
from which oil is drawn as vacuum gas oil (VGO), part of which is sent to the column
as the refl ux and the rest to storage. Condensates from the hot well and the separator
drum are drained to the sewer or water collection system. A few plates below the top
plate of the column, an additional VGO is drawn and sent to the diesel/gas oil pool. SO
is the next vacuum distillate, which is drawn a few plates below the gas oil draw plate.
Similarly, the other vacuum distillates drawn from the plates below are light oil (LO),
intermediate oil (IO), and heavy oil (HO) in this sequence. LO is sent to the vis-breaking
unit for the production of low viscous fuel oils, whereas SO, IO, and HO distillates are
further stripped in a side stripper by steam to remove the lighter components to adjust
the fl ash points. The bottom residue from the tower is called the short residue (SR),
which is stripped by the bottom steam followed by cooling through a steam generator
and sent for storage in the deasphalting unit. A portion of the hot vacuum distillate is
drawn from the column and returned back after cooling to control the heat load of the
column. This stream is called the pump around. Unlike circulating refl uxes in the atmospheric
column, pump around is only one stream in the vacuum column. To aid washing
of the HO fraction, 4%–5% of the feed RCO is overfl ashed. It is to be mentioned that
SO, IO, and HO are the lube oil base stocks (LOBS), which are the main ingredients of
lubricating oils in the market. Valuable lube oil stock, known as bright stock, is obtained
from the SR by solvent deasphalting. However, the quality of vacuum distillates varies
from crude to crude and, as a result, many crudes may not yield LOBS, but are converted
to fuel products. It is commonly found that most of the Middle East or Gulf crudes are suitable for the
manufacture of LOBS from vacuum distillates.

3. VIS-BREAKING
Vis-breaking or viscosity breaking is a mild thermal cracking unit that produces
low viscosity fuel oil from a high viscosity oil stock. In this method, the feedstock
is usually a mixture of high vacuum distillates and residues, even asphalt, heated
in a furnace at a cracking temperature (slightly above 400°C) at a pressure above
atmosphere for a short time and quickly quenched and fl ashed in a plated column.
Suffi cient steam is used to separate the cracked light hydrocarbons. Products include
gases, gasoline (VB gasoline or naphtha), gas oil (VB gas oil), and low viscous
fuel oil or furnace oil as the major product. A typical vis-breaking unit is shown in
Figure 3.25. As shown in the fi gure, heavy viscous vacuum oils, residue from the vacuum distillation
unit, and asphalt from a propane deasphalting unit are the feedstocks,
which are preheated by hot products followed by heating in a tube-still furnace
and then fl ashed in a distillation column. Top vapours enter a stabiliser column
to separate the gases and VB naphtha components. Gases are further scrubbed in an
absorber tower by VB gas oil from the main distillation column. Gases leaving the
absorber tower are used as fuel gas and the rich gas oil stream containing scrubbed
hydrocarbons from the gases is recycled back to the main fractionator column. The
bottom of the main fractionator column is the VB tar (black oil) which is the cheapest
and major fuel for the industrial furnaces.
The by-products are VB gas oil and VB naphtha. VB gas oil is mixed with the
straight run, vacuum, light cycle gas oils, etc., for HSD as the fi nal product. VB naphtha
has medium octane number and is blended with high octane components like
cat cracked gasoline and reformate. Since the products from this unit contain much
mercaptans and unsaturated hydrocarbons, meroxing or desulfurising is essential.
Catalytic hydrodesulfurisation may be benefi cial as far as the removal of sulfur and
olefi ns/di-olifins is concerned, but at the cost of an octane number.

4. liquid liquid EXTRACTION

If two liquids, a solvent and a solute, are in a homogeneous solution and a third liquid
is introduced into the solution, there will be two liquid layers separated into two
homogeneous solutions as shown in Figure 10.1. This type of phenomenon will occur
only for certain selected third liquids, which solubilise any one or both of the components,
which were formerly in the homogeneous solution. Phase separation occurs
due to the difference in density of the resulting solutions. This phenomenon is utilised
for separating two miscible liquid components from a solution and such a method is
called extraction. If the solute (A), the carrier liquid (B) in the feed mixture, and the
pure solvent (C) are brought in intimate contact by thorough mixing, the solute will
transfer to the solvent due to the concentration gradient set up between the feed and
the solvent. This transfer (mass transfer) process will continue until the equilibrium
concentration of the solute between the feed and the solvent is achieved, as long as the
feed and the solvent are in intimate contact.
Extraction is applicable for separating components that are diffi cult to separate by
distillation, settling, or other means. For instance, if the boiling points of the components
are very close or the desired components are too sensitive to high temperature extraction should be
used as the best method for separation. When all the components
involved in extraction are in liquid phases, the process is known as liquid extraction.
While the feed is a solid mixture containing the solute, extraction by a liquid solvent
is carried out and the process is known as leaching. For example, separation of
aromatic hydrocarbons from vacuum distillates by furfural (solvent) is an example of
liquid extraction, whereas removal of paraffi nic hydrocarbons from waxy distillates
by ketone (solvent) is an example of leaching. In refi neries and petrochemical plants,
extraction processes also involve more than one solute and more than one solvent.

10.2 EXTRACTION PROCESS

Any extraction process requires three operating steps, i.e., mixing, separating, and solvent
recovery. The solvent and the feed must be mixed intimately to transfer the solute
to the solvent. After mixing, the fi nal mixture is allowed to settle, while two phases
containing the solvent rich phase or the extract and the solvent lean phase or raffi nate
are separated. These phases will separate by gravity or by centrifuge settler. Usually, the
solvent is also partially soluble in the feed and vice versa and as a result both the extract
and raffi nate phases will contain solvent, solute, and the carrier components. The next
step will be to recover the solvent from these phases usually by distillation. Finally, the
extract phase will yield solute and the raffi nate phase will be the feed liquids nearly free
from solutes. The success of any extraction process depends on various factors as listed
below.

5.SOLVENT DEWAXING:
Vacuum residue after vis-breaking is sent for dewaxing to adjust the pour point of the oil. Normal
paraffinic hydrocarbons present in the oil have a high solidification temperature and form
wax as the solid or semi-solid mass of hydrocarbons. There are paraffinic molecules that can solidify
even at room temperature. Since lubricating oil is used at various
temperatures, ranging from very low to very high temperatures, it is essential
that lubricating oil does not solidify in this range of temperatures. Hence, the pour
point of lube oil must be low.
Though paraffins are responsible for wax formation (wax
is defined as the hydrocarbon matter that solidifi es at a temperature below –20°C (or
the lowest temperature of the environment determined by the usage). Wax-forming
hydrocarbons are selectively removed by low temperature freezing and separation.
This is usually carried out by mixing the feed oil with a solvent, such as methyl
ethyl ketone, benzene, or toluene, mixed in various proportions to prevent crystallisation
Of the wax-forming molecules in the precoolers and chillers, until they are
separated from the solvents along with the desired oil components through a filter.
A typical dewaxing plant, uses a vacuum drum filter where
the solvent–oil mixture is sprayed over a filter cloth on a rotary drum enclosed in
an inert atmosphere. The wax crystallises over the filter cloth and is scraped out
with a scraping blade (also known as doctor’s knife) in a continuous manner. The
drum is divided into four chambers, for filtering, washing, purging, and scraping.
Each section is connected separately with the vacuum, inert gas or steam, solvent,
and filtrate oil collection systems through a rotary valve arrangement. The drum is
partially submerged in a vessel containing the oil–solvent mixture and, as it rotates,
the various chambers come in contact in succession. When the filtering zone comes
in contact with the oil–solvent mixture, separation of the wax from oil starts and
a wax layer is developed on the surface of the filter cloth. As this section is about to leave the oil–
solvent level, the wax cake is completely developed over the filter
cloth and the majority of oil is dewaxed. As the drum enters the washing section, an
additional solvent is sprayed over the wax cake, which removes the entrapped oil, if
any, and is removed by the vacuum connection of that section. As the cake reaches
the purging section, inert gas purges the cake adhering to the cloth surface in order
to loosen the wax cake to aid easy removal of the wax in the next section. This helps
prevent the pores of the filter cloth from being plugged by wax. As the scraping section
is entered, loose wax cake travels under a blade and is scraped from the cloth.
Sometimes, steam is also purged to free the pores of the cloth. The scraped wax is
then passed over a steam-heated screw conveyor to a wax collection pit.

6. HYDROFINISHING
Dewaxed oil from the dewaxing unit contains sulfur, oxygen, nitrogen, and organometallic compounds,
which must be removed to improve the quality of LOBS. Sulfur is present as mercaptans and as
heteroatomic hydrocarbons in oil and is responsible for the corrosive effects. Nitrogen compounds are
responsible for the colour of the lube. Metallic compounds are responsible for unwanted deposition and
may cause degradation of metallic surfaces in contact with the lube. Corrosiveness due to the presence
of oxygen compounds for the formation of acid may occur. High molecular weight olefinic or
unsaturated compounds, especially diolefins, may give rise to poor oxidation stability. In the
hydrofinishing unit, catalytic hydrogenation is carried out in a fixed bed
reactor. A nickel–molybdenum or tungsten catalyst is used at a high partial pressure
of hydrogen. Temperature and pressure are maintained at around 350°C and
50–80 kg/cm2, depending on the feedstock to be treated.

7. COKING
The coking unit of a refinery yields petroleum coke, which is heavily condensed hydrocarbon with more
than 90% carbon. This high carbon stock is used in the metallurgical and graphite industries for
extraction of metals from ores and also as a clean fuel. The coking unit uses various methods depending
on the properties required by the users. Delayed coking and fluid coking plants are commonly employed
in refineries.In the delayed coking unit, feedstock is heated in a furnace to a temperature of
around 480°C–500°C at high velocity before sending to a coking drum where a long residence time
allows the coking reactions to go to completion, thereby maximizing coke formation. Once the coke
drum is filled, another empty coking drum is pressed into service, the filled drum is isolated and coke is
cut off by a high velocity water jet. In any such unit, a minimum of two coking drums or chambers are
required, however more drums or high volume chambers can also be used. In the fluid coking method, a
fluidised bed of coke is used by atomising feedstock with steam and the high temperature is maintained
by partially burning the coke particles in a fluidised bed burner.
8. Flash Point
The flash point is defined as the temperature of the oil at which it momentarily flashes in the presence
of air and the igniting source. This is determined in the laboratory using a standard cup, standard flame,
and under standard atmospheric conditions. There are two standard test methods for measurement—
the open cup method (Abel’s method) and the closed cup method (Pensky–Mertinus method). In either
test, oil is taken in a closed container provided with a stirrer and a heater.The temperature of the oil in
the bath is measured by a thermometer. The oil is heated at the rate of 5°C–6°C per minute and a
standard flame is introduced every 30 sec. The temperature at which a momentary flash occurs is noted
as the flash point.

9. Octane Number
Engine performance is measured by the maximum power generated and the rate at which it is
developed at different engine speeds. If the rate of power development is not uniform with speed,
rather it fluctuates, then this type of situation is called knocking or hammering of the engine. Several
experiments found that the composition of MS plays the main role in knocking. If MS contains more
propane,butane (short chain hydrocarbons), iso-octane (branched chain hydrocarbons), benzene,
toluene, xylenes, and aromatics (ring compounds) in the boiling range of MS then the rate of power
development is smooth without knocking, whereas the long chain hydrocarbons give rise to severe
knocking if present in the fuel in substantial amounts. Since MS is a mixture of all the short or long chain,
branched, and ring hydrocarbons, it is common practice to use iso-octane as the fingerprint for
measuring the relative engine performance of the mixture. Specification of MS as far as engine
performance is concerned is denoted by octane number
with the decrease in the proportion iso-octane in the fuel. The octane number of the
MS sample, therefore, falls within 0 and 100. This is measured in a standard engine,
known as the co-operative fuel research (CFR) engine.
However, the octane number may be greater than 100, which is called the performance
 An engine test is carried out at two different speeds and the octane numbers are defined as the
research octane number (RON) and the motor octane number (MON), which are conducted at two
different speeds, 600 and 900 rpm, respectively. However, tested octanes may not correspond to real
performance when the road conditions differ. RON is more applicable for city driving whereas MON is
applicable for highway driving. The octane number falls with the increase in speed, which is why MON is
always less than RON for the same MS fuel.

10. Cetane Number

It has been found that paraffinic hydrocarbon has a lower autoignition temperature than that of
aromatics. Therefore, if diesel oil is rich with aromatic hydrocarbons than the paraffinic counterparts,
most of the oil will be unburnt at the beginning and will simultaneously burn suddenly when the
temperature rises due to the combustion of paraffinic hydrocarbons. This type of situation will give rise
to non-uniform pressure (shock wave or knocking) in the engine. Knocking quality of diesel oil is
measured by cetane number, which is defined as the percentage of normal cetane (a straight chain
hydrocarbon) in a mixture of n-cetane and α-methyl naphthalene (an aromatic hydrocarbon), which
gives the same performance as that of the diesel sample.

11. Diesel Index

The presence of paraffi nic hydrocarbons in diesel may be related by the aniline
point, which is the temperature at which aniline solubilises the fuel in equal amounts and a
homogeneous mixture results. The greater the paraffi n content, the higher the
aniline point. Also, the API gravity of oil increases as the paraffi n content rises.
With the help of these properties, the diesel index (DI) is given as
DI = API × aniline point in °F ∕ 100.

13. Pour Point

The pour point of a liquid is the temperature below which the liquid loses its flow characteristics. In
crude oil a high pour point is generally associated with a high paraffin content, typically found in crude
deriving from a larger proportion of plant material.