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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
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.
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.