INTRODUCTION TO PETROLEUM REFINING

HIPAL
 INTRODUCTION

 Refining adds value by converting crude oil

 into a range of refined products, including transportation fuels.
 The primary economic objective in refining is to maximize the value
added in converting crude oil into finished products.
 Petroleum refineries are large, capital-intensive manufacturing facilities
with extremely complex processing schemes. They convert crude oils and
other input streams into dozens of refined (co-)products, including:
 ♦ Liquified petroleum gases (LPG)
 ♦ Gasoline
 ♦ Jet fuel
  ♦ Kerosene (for lighting and heating)
 ♦ Diesel fuel
 ♦ Petrochemical feedstocks
 ♦ Lubricating oils and waxes
 ♦ Home heating oil
INTRODUCTION
 ♦ Fuel oil (for power generation, marine fuel, industrial and
district heating)
 ♦ Asphalt (for paving and roofing uses).

CRUDE OIL
THE CHEMICAL CONSTITUENTS OF CRUDE OIL

 Each crude oil is unique and is a complex mixture of thousands of

compounds. Most of the compounds in crude oil are hydrocarbons (organic
compounds composed of carbon and hydrogen atoms).
 Other compounds in crude oil contain not only carbon and hydrogen, but
also small (but important) amounts of other (“hetero”-) elements –most
notably
 sulfur,
 as well as nitrogen and
 certain metals (e.g., nickel, vanadium, etc.).
 The compounds that make up crude oil range
from the smallest and simplest hydrocarbon
molecule
 – CH4 (methane) – to large, complex
molecules containing up to 50 or more
carbon atoms (as well hydrogen and hetero-
elements).
CRUDE OIL

IMPORTANT CHARACTERIZATION PROPERTIES

 - Viscosity Numerous important feed and product characterization properties in refinery engineering
include
 - API gravity
 - Watson Characterization factor

 - Sulfur content
 - True boiling point (TBP) curve
 - Pour point
 - Flash and fire point
 - ASTM distillation curve
 - Octane number
CRUDE OIL

API GRAVITY LIGHT OR HEAVY CRUDE OIL

 API gravity Density (light, heavy) API gravity of petroleum fractions is a measure of density of the stream.
Usually measured at 60 oF, the API gravity is expressed as

 Specific gravity = ρLiquid / ρwater

 Therefore, crude oil with high values of API gravity are expensive to procure due to their quality.
 In other words, higher values of API gravity indicate lower specific gravity and therefore lighter CRUDE
 The higher the number the lighter the crude oil.
 Generally, the lighter crudes are more valuable since they’ll produce more of the higher valued products.
 crude oils or refinery products and vice-versa. As far as crude oil is concerned, lighter API gravity value is
desired as more amount of gas fraction, naphtha and gas oils can be produced from the lighter crude oil than
with the heavier crude oil.
CRUDE OIL

WATSON CHARACTERIZATION FACTOR


The Watson characterization factor is usually expressed as
 K = (TB)1/3 /specific gravity
 Where TB is the average boiling point in degrees R taken from five temperatures corresponding to 10,
30, 50, 70 and 90 volume % vaporized
 Typically Watson characterization factor varies between 10.5 and 13 for various crude streams.
 A highly paraffinic crude typically possesses a K factor of 13.
 On the other hand, a highly naphthenic crude possesses a K factor of 10.5.
 Therefore, Watson characterization factor can be used to judge upon the quality of the crude oil in terms
of the dominance of the paraffinic or naphthenic components.
CRUDE OIL

SULFUR CONTENT- SOUR OR SWEET CRUDE OIL

 Since crude oil is obtained from petroleum reservoirs, sulphur is present in the crude oil.
 Usually, crude oil has both organic and inorganic sulphur in which the inorganic sulphur dominates the composition.
Typically, crude oils with high sulphur content are termed as sour crude.
 On the other hand, crude oils with low sulphur content are termed as sweet crude.
 Typically, crude oil sulphur content consists of 0.5 – 5 wt % of sulphur.
 Crudes with sulphur content lower than 0.5 wt % are termed as sweet crudes.
 It is estimated that about 80 % of world crude oil reserves are sour.
 The sulphur content in the crude oil is responsible for numerous hydrotreating operations in the refinery process.
 Strict and tighter legislations enforce the production of various consumer petroleum products with low quantities of sulphur
(in the range of ppm).
 This indicates that large quantities of inorganic sulphur needs to be removed from the fuel. Typically, inorganic sulphur
from various intermediate product streams is removed using hydrogen as hydrogen sulphide.
 A sour taste with the smell of rotten eggs indicated a high sulfur content. It is through this old testing method that the terms
"sweet crude" and "sour crude" came to be.
 West Texas Intermediate, or WTI crude oil, North Sea Brent Crude
 North America: Alberta (Canada), United States' portion of the Gulf of Mexico, Alaska and Mexico. South America:
CRUDE OIL
TBP/ASTM DISTILLATION CURVES

 The most important characterization properties of the crude/intermediate/product

streams are the TBP/ASTM distillation curves. Both these distillation curves are
measured at 1 atm pressure.
 In both these cases, the boiling points of various volume fractions are being measured.
 However, 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 100 trays and very high reflux ratio, the ASTM distillation is measured in a single
stage apparatus without any reflux.
CRUDE OIL

VISCOSITY

 Viscosity is a measure of the flow properties of the refinery stream.

 Typically in the refining industry, viscosity is measured in terms of centistokes (termed
as cst) or saybolt seconds or redwood seconds.
 Usually, the viscosity measurements are carried out at 100 oF and 210 oF.
 Viscosity is a very important property for the heavy products obtained from the crude
oil. The viscosity acts as an important characterization property in the blending units
associated to heavy products
CRUDE OIL

FLASH AND FIRE POINT

 Flash and fire point are important properties that are relevant to the safety and
transmission of refinery products.
 Flash point the lowest temperature at which a liquid (usually a petroleum product)
will form a vapour in the air near its surface that will “flash,” or briefly ignite, on
exposure to an open flame.
 The flash point is a general indication of the flammability or combustibility of a liquid.

 Fire point : fire point of a fuel is the lowest temperature at which the vapour of that fuel
will continue to burn for at least five seconds after ignition by an open flame
CRUDE OIL

POUR POINT

When a petroleum product is cooled, first a cloudy appearance of

the product occurs at a certain temperature.
 This temperature is termed as the cloud point.
 Upon further cooling, the product will ceases to flow at a
temperature.
 This temperature is termed as the pour point.
 Both pour and cloud points are important properties of the
product streams as far as heavier products are concerned. For
heavier products, they are specified in a desired range
CRUDE OIL

OCTANE NUMBER

 Octane number Though irrelevant to the crude oil stream, the octane number is an
important property for many intermediate streams that undergo blending later on to
produce automotive gasoline, diesel etc.

 The octane number (ON) is a measure of the knock resistance of gasoline. It defines a
numerical value from 0 to 100, and describes the behavior of the fuel in the engine
during combustion.
 While iso-octane (2,2,4-Trimethylpentane)was given an octane number of 100, n-
heptane is given a scale of 0. Therefore, the octane number of a fuel is equivalent to a
mixture of a iso-octane and n-heptane that provides the same compression ratio in a fuel
engine.
 Thus an octane number of 80 indicates that the fuel is equivalent to the performance
characteristics in a fuel engine fed with 80 vol % of isooctane and 20 % of n-heptane.
 Octane numbers are very relevant in the reforming, isomerisation and alkylation
CRUDE OIL
CRUDE CHEMISTRY
 Fundamentally, crude oil consists of
 84 – 87 wt % carbon,
 11 – 14 % hydrogen,
 0 – 3 wt % sulphur,
 0 – 2 wt % oxygen,
 0 – 0.6 wt % nitrogen and
 metals ranging from 0 – 100 ppm.
 Understanding thoroughly the fundamentals of crude chemistry is very important in
various refining processes.
 The existence of compounds with various functional groups and their dominance or
reduction in various refinery products is what is essentially targeted in various chemical
and physical processes in the refinery.
CRUDE OIL
CRUDE CHEMISTRY

Based on chemical analysis and existence of various functional groups, refinery crude
can be broadly categorized into about 9 categories
Paraffins:
 Olefins:
 Naphthenes:
 Aromatics:
 Napthalenes:
 Organic sulphur compounds:
 Oxygen containing compounds:
 Resins:
 Asphaltenes:
CRUDE OIL

CRUDE CHEMISTRY
PARAFFINS:

Paraffins refer to alkanes such as

methane, ethane, propane, n and iso butane, n and iso pentane.
These compounds are primarily obtained as a gas fraction from the crude distillation unit.
CRUDE OIL

CRUDE CHEMISTRY
OLEFINS:
 Alkenes such as
 ethylene,
 propylene and
 butylenes are highly chemically reactive. They are not found in
mentionable quantities in crude oil but are encountered in some refinery
processes such as alkylation.
CRUDE OIL

CRUDE CHEMISTRY
NAPHTHENES

 Naphthenes or cycloalkanes such as cyclopropane, methyl cyclohexane are

also present in the crude oil.
 These compounds are not aromatic and hence do not contribute much to
the octane number.
 Therefore, in the reforming reaction, these compounds are targeted to
generate aromatics which have higher octane numbers than the naphthenes
CRUDE OIL

CRUDE CHEMISTRY
AROMATICS:
 Aromatics such as
 benzene,
 toluene
 o/m/p-xylene are also available in the crude oil.
 These contribute towards higher octane number products and the target is
to maximize their quantity in a refinery process.
CRUDE OIL

CRUDE CHEMISTRY
NAPTHALENES:

Polynuclear aromatics such as naphthalenes consist of two or three or more

aromatic rings. Their molecular weight is usually between 150 – 500.
CRUDE OIL

CRUDE CHEMISTRY
ORGANIC SULPHUR COMPOUNDS:

 Not all compounds in the crude are hydrocarbons consisting of hydrogen

and carbon only.
 Organic sulphur compounds such as thiophene,
 pyridine also exist in the crude oil.
CRUDE OIL
OXYGEN CONTAINING COMPOUNDS:

 These compounds do not exceed 2 % by weight in the crude oil.

 Typical examples are acetic and benzoic acids.
 These compounds cause corrosion and therefore needs to be effectively
handled.
CRUDE OIL

RESINS:

 Resins are polynuclear aromatic structures supported with side chains of

paraffins and small ring aromatics.
 Their molecular weights vary between 500 – 1500.
 These compounds also contain sulphur, nitrogen, oxygen, vanadium and
nickel.
CRUDE OIL

ASPHALTENES:

 Asphaltenes are polynuclear aromatic structures consisting of 20 or more

aromatic rings along with paraffinic and naphthenic chains.
 A crude with high quantities of resins and asphaltenes (heavy crude) is
usually targeted for coke production.
TYPES OF OIL REFINERY

 there are four types of refineries

 – topping,
 hydro-skimming,
 conversion, and
 deep conversion refineries.
 Depending on the market a refiner is aiming at,
each refinery has its unique design to ensure their
production conforms to their host country’s set
standards
TYPES OF OIL REFINERY
TOPPING REFINERY
 Topping refinery is a processing plant with a
simple configuration.
 Constructed primarily for preparing raw materials
for manufacturing petrochemicals and industrial
fuels
 a topping refinery serves better in areas where
there are less refining regulations.
 they produce high volumes of poorly-refined oil
because they lack the required processing units to
reduce sulfur levels.
TYPES OF OIL REFINERY
TOPPING REFINERY

 topping refineries comprise facilities such as

 tanks,
 distillation units,
 gas,
 light hydrocarbons recovery facilities, and other
necessary utility systems.
HYDRO-SKIMMING OIL REFINERY

 Hydro-skimming refineries refine better than

topping refineries because of the addition of
hydrotreating and reforming units to the basic
configuration that makes up a topping refinery.
 hydro skimming plants can produce refined
products from little feedstocks as well as high
octane gasoline.
 Also, it can produce naphtha as well as hydrogen
as by-products.
 HYDRO-SKIMMING OIL REFINERY

 The addition of a few other functional units such as hydro-treating,

hydro-cracking, and a few others to hydro-skimming refineries make
them more efficient than topping refineries.
 hydro-skimming plants may not deliver high-quality petroleum
products as most of their outputs are usually residual fuels.
 Also, their low-quality output remains a challenge because more
consumers are shying away from sulfur-filled petroleum products.
 TYPES OF OIL REFINERY
CONVERSION OIL REFINERIES

 Also known as cracking refineries, conversion refineries are refining plants

that have all basic units that make up both topping and hydro-skimming
refineries as well as gas oil conversion units.
 Also, additional units such as Olefin conversion plant and coking units are
what makes them more efficient than hydro-skimming plants.
 Furthermore, it has an additional beneficial feature which is reductions in the
production of residual fuels. In other words, conversion oil refining plant
produces lighter fuels such as gasoline, jet fuel, and diesel.
 TYPES OF OIL REFINERY
DEEP CONVERSION REFINERIES

 A deep Conversion refinery is a combination oF all

components of a conversion refinery, and an additional unit
known as the coking unit.
 The coking unit makes it possible to treat and convert
extremely heavy crude oil fractions into lighter products.
CRUDE OIL

REFINERY PROCESSES

 There are about 22 units in the flowsheet which themselves are complex enough
to be regarded as process flow sheets.
 However, for the convenience of our understanding, we present them as units or
blocks which enable either distillation in sequence or reactive transformation
followed by distillation sequences to achieve the desired products.
 Crude distillation unit (CDU)
 Vacuum distillation unit (VDU)
 Thermal cracker
 Hydrotreaters
 Fluidized catalytic cracker
CRUDE OIL

REFINERY PROCESSES

 Separators
 Naphtha splitter
 Reformer
 Alkylation and isomerisation
 Gas treating
 Blending pools
 Stream splitters
REFINERY PROCESSES

 In this section, we present a brief overview of the

crude distillation process.
 The first essential task for the crude oil consisting
of more than 108 compounds is to separate its
major components based on boiling point
differences.
 REFINERY PROCESSES
CRUDE DISTILLATION UNIT (CDU)
 It consists of the following important sub-processes:
 Crude desalter
 Furnace
 Pre-flash column
 Crude distillation column supplemented with side
columns. These columns produce the desired
products
 Pump around heat exchanger units
 Heat exchanger network that facilitates energy
recovery from hot product and reflux streams to heat
the crude oil.
 REFINERY PROCESSES
CRUDE DESALTER

 Crude oil consists of dissolved salts and they tend to cause fouling and
corrosion in various process equipments. Therefore, dissolved salts
need to be removed using a separation process
 The crude desalting unit is a separation process. Here, water along with
other trace chemicals such as caustic and acid are allowed to enter a
mixing unit along with the crude oil.
 The mixture of crude oil and water is subsequently passed through an
electrostatic precipitator cum gravity settler. The electrostatic field
enables the agglomeration of water droplets and aids faster gravity
settling.
 An essential issue for the good performance of crude desalter is the
temperature of the operation. Usually, high efficiency of salt removal is
possible between 100 – 300 oF.
 Therefore, the crude oil is heated to about 250 oF before it
enters the desalter unit.
 The clean desalted crude oil flows from the top of the gravity
settler and the water along with other dissolved impurities is
removed as a bottom product from the gravity settler unit.
 A high degree of salt removal is desired (95 – 99% removal of
the dissolved salt in the crude oil). Usually, a two stage
desalting process is deployed. When higher salt removal
efficiencies are desired, three stage units are deployed.
 REFINERY PROCESSES
FURNACE

 The furnace is an important constituent in the crude distillation unit

 Here, fuel oil and fuel gas (heavier products) obtained from the refining
process itself are burnt to increase the crude oil temperature.
 Typically in refineries, the crude oil is heated to a temperature that
enables overflash conditions in the main crude distillation column.
 The concept of overflash is that the crude is heated to such a
temperature that enables an additional 5 % vaporization with respect to
the residue product. In other words, the residue fraction vapours
amounting to 5 % of the total volume of the crude oil are desired.
 Depending upon the quality of the crude, the desired temperature for the
crude oil is about 600 - 700 oF.(315- 370oC)
 REFINERY PROCESSES
 Pre-flash column
 The crude oil enters the pre-flash column after leaving the furnace
 The pre-flash tower separates the lighter fractions of the already heated crude
oil.
 The heavier fractions of the crude oil leave from the bottom section of the pre-
flash tower.
 Both lighter and heavier streams emanating from the pre-flash tower are fed to
the main crude distillation column at various sections
 Pre-flash column enables better refluxes in the main column by distributing the
streams effectively between various processing zones of the crude oil.
 Pre-flash column may or may not be included i.e., it is optional. In other
words, the pre-flash column can be avoided and the heated crude oil from the
 REFINERY PROCESSES
MAIN AND SECONDARY DISTILLATION
COLUMNS

 The main column consists of 45 trays and the secondary columns

(side strippers) consist of 4 trays each. Three side strippers are
used to strip the light ends from kerosene, LGO and HGO
products.
 The main column has two sections that are distinguished with
respect to a flash zone.
 The flash zone is where the crude oil partially vaporized is fed to
the main column.
 REFINERY PROCESSES
MAIN AND SECONDARY DISTILLATION
COLUMNS

 There are about 4 trays below the flash zone and 41 trays above
the flash zone of the main column.
 The bottom most tray (residue stripping tray) is numbered as 1
and the top tower tray is numbered as 45.
 Trays 1 to 4 process the atmospheric residue portion of the crude
in the section below the flash zone.
 REFINERY PROCESSES
MAIN AND SECONDARY DISTILLATION COLUMNS

 Trays 5 to 10 (6 trays above the flash zone) process

the HGO product portion of the crude.
 From tray 10, HGO draw off product is taken out (as
liquid) and enters the HGO side stripper unit.
 From tray 10 as well, the liquid stream is drawn and
sent to tray 12 via a bottom pump around unit that
enables cooling of the liquid stream.
 The steam + light ends from the HGO side stripper
enter tray 11 of the main column.
 Trays 13 to 22 (10 trays above the HGO processing zone)
process the LGO product portion of the crude.
 From tray 22, LGO draw off product is taken (as liquid) and sent
to the LGO side stripper unit.
 Also, from tray 22, another liquid stream is taken out and sent to
tray 24 via a top pump around unit (TPA) that enables cooling of
the liquid stream.
 The steam + light ends from the LGO side stripper enter tray 23
of the main column
REFINERY PROCESSES
MAIN AND SECONDARY DISTILLATION
COLUMNS

 Trays 24 to 34 (10 trays above the LGO processing

zone) process the kerosene product portion of the
crude.
 From tray 34, the kerosene draw off stream is taken
and sent to the kerosene side stripper unit. The steam
+ light ends of the kerosene side stripper enter tray
35.
 Trays 34 to 45 (12 trays above the Kerosene
processing zone) process the naphtha product portion
of the crude.
 It is interesting to note that tray 34 is regarded as a tray
processing both LGO as well as naphtha processing zone.
This is because there is no pump around associated to the tray
34.
 Where pump around is associated, that tray is often ignored in
counting, as it affects to a large extent the tray hydraulics and
contributes less towards the separation of the components.
 REFINERY PROCESSES
MAIN AND SECONDARY DISTILLATION
COLUMNS

 It is interesting to note that steam enters main

column at trays 1, 11, 23, 35 and therefore is
present along with the vapor stream along with
the hydrocarbons.
 Therefore, steam balances throughout the
column are very important.
 The cold naphtha stream obtained from the
phase separator is sent back to the main
column as reflux stream.
 REFINERY PROCESSES

 Heat exchanger networks

 Two heat exchanger networks exist in the crude distillation unit, one
before the crude desalter and one after the crude desalter.
 The heat exchanger networks facilitate energy recovery from hot
product, naphtha+steam vapor and reflux streams to heat the crude oil in
an indirect heat transfer mode i.e, using heat exchangers.
 Therefore, the design and operation of a heat exchanger network is very
important in the crude distillation unit.
REFINERY PROCESSES
 Further, it needs to be understood that the naphtha heat
integrated condenser is a partial condenser whereas all
others are heat exchangers without any phase change
streams.
 The heat exchanger networks enable to increase the crude
oil stream temperature to about 200 – 230 oC which is
significantly higher than the crude oil source temperature
(about 20 – 30 oC).
 Crude distillation units without heat exchanger networks
have higher furnace load targets. They also cause more
pollution due to burning more fuel oil and fuel gas
streams.
VACUUM DISTILLATION UNIT (VDU)

 The atmospheric residue when processed at lower pressures does not allow
decomposition of the atmospheric residue and therefore yields LVGO, HVGO and
vacuum residue.
 The LVGO and HVGO are eventually subjected to cracking to yield even lighter
products.
 The VDU consists of a main vacuum distillation column supported with side strippers to
produce the desired products.
 The pressure maintained is about 25 – 40 mm Hg. The temperature is kept at around 380
– 420oC
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