OIL

REFINERY
PROCESSES
LECTURE: ALIYA
TEMIRKHAN
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 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.
∙ 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.
Atmospheric distillation
Simple crude distillation
Vacuum distillation
∙ To further distill the residuum 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. The internal
designs of some vacuum towers are different from atmospheric towers in
that random packing and demister pads are used instead of trays.
∙ 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 from the first vacuum tower not used
for deasphalting.
∙ Vacuum towers are typically used to separate catalytic cracking feedstock
from 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.
∙ Vacuum residue is fed to a countercurrent deasphalting tower.
Alkanes dissolve in propane whereas asphaltenic materials
(aromatic compounds), ‘coke-precursors’ do not.
∙ Asphalt is sent for thermal processing.
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.
∙ In one type of process, the feedstock is washed with a liquid in which the
substances to be removed are more soluble than in the desired resultant
product. In another process, selected solvents are added to cause impurities
to precipitate out of the product. In the adsorption process, highly porous
solid materials collect liquid molecules on their surfaces.
∙ 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.
 Solvent extraction
∙ Electric precipitation may be used for separation of inorganic compounds.
∙ The solvent is regenerated for reused in the process.
∙ The most widely used extraction solvents are phenol, furfural, and cresylic
acid.
∙ Other solvents less frequently used are liquid sulfur dioxide, nitrobenzene,
and 2,2' dichloroethyl ether.
∙ The selection of specific processes and chemical agents depends on the
nature of the feedstock being treated, the contaminants present, and the
finished product requirements.
Aromatic solvent extraction unit
 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.
The oil refining process starts with a fractional distillation column.

The problem with crude oil is that it contains hundreds of different HC

We have to separate the different types of hydrocarbons to have anything useful. Fortunately
there is an easy way to separate things, and this is what oil refining is all about.

Different hydrocarbon chain lengths all have progressively higher boiling points, so they can
all be separated by distillation.

This is what happens in an oil refinery-in one part of the process, crude oil is heated and the
different chains are pulled out by their vaporization temperatures.

Each different chain length has a different property that makes it useful in a different way.
To understand the diversity contained in crude oil, and to understand why refining crude oil is
so important in our society, look through the following list of products that come from crude
oil:
Petroleum gas-used for heating, cooking, making plastics
small alkanes(1 to 4 carbon atoms)
commonly known by the names methane, ethane, propane, butane
boiling range = less than 104 degrees Fahrenheit / 40 degrees
Celsius
often liquified under pressure to create LPG (liquifiedpetroleum
gas)
Naphtha or Ligroin-intermediate that will be further processed to
make gasoline
mix of 5 to 9 carbon atom alkanes
boiling range = 140 to 212 degrees Fahrenheit / 60 to 100 degrees
Celsius
Gasoline-motor fuel-liquid
mix of alkanes and cycloalkanes (5 to 12 carbon atoms)
boiling range = 104 to 401 degrees Fahrenheit / 40 to 205 degrees Celsius
Kerosene-fuel for jet engines and tractors; starting material for making other
products-liquid
mix of alkanes(10 to 18 carbons) and aromatics
boiling range = 350 to 617 degrees Fahrenheit / 175 to 325 degrees Celsius

Gas oilor Diesel distillate-used for diesel fuel and heating oil; starting
material for making other products-liquid
alkanes containing 12 or more carbon atoms
boiling range = 482 to 662 degrees Fahrenheit / 250 to 350 degrees Celsius
Lubricating oil-used for motor oil, grease, other lubricants liquid
long chain (20 to 50 carbon atoms) alkanes, cycloalkanes, aromatics
boiling range = 572 to 700 degrees Fahrenheit / 300 to 370 degrees Celsius
Heavy gasor Fuel oil-used for industrial fuel; starting material for making
other products liquid
long chain (20 to 70 carbon atoms) alkanes, cycloalkanes, aromatics
boiling range = 700 to 1112 degrees Fahrenheit / 370 to 600 degrees
Celsius
Residuals-coke, asphalt, tar, waxes; starting material for making other
products
solid
multiple-ringed compounds with 70 or more carbon atoms
boiling range = greater than 1112 degrees Fahrenheit / 600 degrees Celsius
You may have noticed that all of these products have different sizes and
boiling ranges. Chemists take advantage of these properties when refining
oil.
 Refinery Products
•Knowledge of the physical and chemical properties of the petroleum products is necessary
for an understanding of the need for the various refinery processes.

Major hydrocarbons in crudeoil:

•Paraffin:series of HC compound having general formula CnH2n+2, i.e.straight chains or
branched chains. Paraffins fromC1 to C40 usually appear in crude oil and represent up to 20%
of crude by volume.
•Since Paraffins are fully saturated (no double bond),they are stable and remain unchanged
over long periods of geological time.
•Examples: methane, ethane, butane, isobutane

•Aromatics: unsaturatedringtype(cyclic) compounds. Naphthalenes are double-ring

aromatic compounds. > 3 aromatic ring are found in heavier fractions of crude oil.
•Some of the common aromatics found in petroleum and crude oils are benzene and its
derivatives with attached methyl, ethyl, propyl,or higher alkyl groups.
Aromatics:
Examples: benzene, methylbenzene

Naphthenes: saturated hydrocarbon groupings (CnH2n), arranged in the form

of closed ring(cyclic).
Can found in all fractions of crude oil except the very lightest one.
Thermodynamic studies show that naphthene rings with five and six carbon
atoms are the most stable naphthenic hydrocarbons.

Cycloalkanes (Naphthenes):
CnH2n, ringed structures with one or more rings contain only single bonds between the
carbon atoms. Examples: cyclohexane, methyl cyclopentane.
 Petroleum Standards
There are a number of international standard organizations that
recommend specific characteristics or standard measuring
techniques for various petroleum products. Some of these
organizations are as follows:

1. ASTM (American Society for Testing and Materials) in the

United States
2. ISO(International Organization for Standardization), which is at
the international level
3. IP(Institute of Petroleum) in the United Kingdom
4. API(American Petroleum Institute) in the United States
 API Gravity
• specific gravity and API gravity refer to the weight per unit
volume (density) at 60°F and 1 atmas compared to water at
60°F and 1 atm.
•Crude oil gravity may range from less than 10°API to over
50°API but most crudes fall in the 20 to 45°API range.
•Generally, a crude with the API gravity of less than 20-22 is
called heavy crude and with API gravity of greater than 33-40
is called light crude. Similarly, if the sulfur content of a crude
is less than 0.5 wt% it is called a sweet oil.
Sulfur Content, wt%
•Sulfur content and API gravity are two properties which have had the greatest influence on
the value of crude oil. 0.1% < S >5%.
•Sour crude (>0.5%) require more extensive processing.

Pour Point, °F (°C)

The pour point of a liquid is the temperature at which it becomes semi-solid and loses its
flow characteristics.
•Thepourpointofthecrudeoil,in°For°C,isaroughindicatoroftherelativeparaffinicityandaromatici
tyofthecrude.
•The lower the pour point, the lower the paraffin content and the greater the content of
aromatics.

Carbon Residue, wt%

•Carbon residue is determined by distillation to a coke residue in the absence of air.
•Related to the asphalt content of the crude and to the quantity of the lubricating oil fraction
that can be recovered.
•In most cases the lower the carbon residue, the more valuable the crude.
Salt Content, lb/1000 bbl
•If the salt content of the crude, when expressed as NaCl, is greater than 10 lb/1000 bbl, it is
generally necessary to desalt the crude before processing.
•If the salt is not removed, severe corrosion problems may be encountered. If residue are
processed catalytically, desalting is desirable at even lower salt contents of the crude.

Characterization Factors
•Correlations between yield and the aromaticity and paraffinicityof crude oils.
•UOP or Watson ‘‘characterization factor’’ (KW) and the U.S. Bureau of Mines ‘‘correlation
index’’ (CI).
Characterization factors
1/3
𝑇𝐵
KW =
𝐺
87.552
CI= + 473.7G – 456.8
𝑇𝐵
where
𝑇𝐵 = mean average boiling points, ° R
G = specific gravity at 60 ° F
Metals Content, ppm
•The metals content of crude oils can vary from a few parts per million to more
than 1000 ppm and, in spite of their relatively low concentrations, are of
considerable importance.

Reid vapor pressure (RVP)

•is the absolute pressure exerted by a mixture at 100 oF(37.8 °C) as determined
by the test method ASTM-D-323 and a vapor-to-liquid volume ratio of 4.The
RVP is one of the important properties of gasolinesand jet fuels.

For a pure compound the freezing point is the temperature at which liquid
solidifies at 1 atmpressure. Similarly the melting point is the temperature that a
solid substance liquefies at 1 atm. A pure substance has the same freezing and
melting points; however, for petroleum mixtures, there are ranges of melting
and freezing points versus percent of the mixture melted or frozen.
Pour point of a petroleum fraction is the lowest temperature
at which the oil will pour or flow when it is cooled without
stirring under standard cooling conditions.

Pour point represents the lowest temperature at which an oil

can be stored and still capable of flowing under gravity. When
temperature is less than pour point of a petroleum product it
cannot be stored or transferred through a pipeline.
Cloud point is the lowest temperature at which wax crystals begin to
form by a gradual cooling under standard conditions. At this
temperature the oil becomes cloudy and the first particles of wax
crystals are observed.
Low cloud point products are desirable under low-temperature
conditions. Wax crystals can plug the fuel system lines and filters,
which could lead to stalling air craft and diesel engines under cold
conditions.
Cloud points are measured for oils that contain paraffins in the form of
wax and therefore for light fractions (naphtha or gasoline) no cloud
point data are reported.
Flash point should not be mistaken with fire point, which is defined
as the minimum temperature at which the hydrocarbon will continue
to burn for at least 5 s after being ignited by a flame.

Auto ignition temperature is the minimum temperature at which

hydrocarbon vapor when mixed with air can spontaneously ignite
without the presence of any external source.

Values of autoignition temperature are generally higher than flash

point. This is particularly important from a safety point of view when
hydrocarbons are compressed. Standard test is ASTMD 2155.
Nitrogen Content, wt%
•A high nitrogen content is undesirable in crude oils because organic nitrogen compounds
cause severe poisoning of catalysts used in processing and cause corrosion problems such as
hydrogen blistering. Crudes containing nitrogen in amounts above 0.25% by weight require
special processing to remove the nitrogen.

Distillation Range
•The boiling range of the
crude gives an indication
of the quantities of the
various products present
Thank you for your
attention