Crude Oil - Characterization

and Components
By
Sudarshan G
 Introduction
• Petroleum, also called crude oil, is a thick and black liquid.

• It is a natural material mainly made of hydrocarbons.

• Most petroleum is found by drilling down through rocks on land or off-shore on the continental shelf. Major producers are

in the Middle East, the Americas, and Russia.

• It supplies 38% of the world's energy and is also used to make petrochemicals.

• The bitumen gives crude oil its dark black color; most of the other chemicals in crude are slightly yellow or colorless.

• Refined petroleum is used as fuels; mainly gasoline (petrol) for cars, diesel fuel for diesel engines used in trucks, trains and

ships, kerosene fuel for jets and as lubricants.

Fundamental components of
Crude Oil
Why Characterize?
• Crude oil comes from different parts of the world and has different physical
and chemical characteristics.
• On the other hand, the products that are produced have to meet market
requirements and as such, should comply with certain specifications.
• Crude oil is a complex liquid mixture made up of a vast number of
hydrocarbon compounds that consist mainly of carbon and hydrogen in
differing proportions.
• In addition, small amounts of organic compounds containing sulphur,
oxygen, nitrogen and metals such as vanadium, nickel, iron and copper are
also present.
• Hydrogen to carbon ratios affect the physical properties of crude oil. As the
hydrogen to carbon ratio decreases, the gravity and boiling point of the
hydrocarbon compounds increases.
Basic Components

Crude oil

Paraffins
Naphthenes Aromatics Aromatics
Paraffins (CnH2n+2)
• Paraffins, also known as alkanes, are
saturated compounds
• Isoparaffins -branched-type hydrocarbons
that exhibit structural isomerization.
• Insoluble in acids-alkalis
• Undergo stable substitution reactions
• Isoparaffins have better antiknock
capabilities
Aromatics (BTX)
• Consist of a stable benzene ring
• Primarily undergo substitution or
addition based on the process conditions
• Better antiknock capabilities for certain
components
Naphthenes
• Also called cycloparaffins
• Saturated Ring components
• Chemically statable in nature
• Insoluble in acids – alkalis.
Olefins
• Non Native to crude
• Usually present in small amounts
• Formed during Processing
• Unsaturated in nature
• Soluble in acids
• Tendency to form polymers and gums
six classes of crude oil that are defined using a ternary diagram
Other major compounds
1. Sulphur
• The Sulphur content -less than 0.05 to more thanc10 wt%
• Crude oil with less than 1 wt % sulphur -low sulphur or sweet
• More than 1 wt% sulphur is referred to as high sulphur or sour.
• FORMS: elemental Sulphur, dissolved H2S, carbonyl sulphide COS,
mercaptans,sulphides and polycyclic sulphides
• Mainly cause corrosion and catalyst poisoning
2. Nitrogen
• Crude oils contain very low amounts of nitrogen compounds.
• The more asphaltic the oil, the higher its nitrogen content.
• They can be responsible for the poisoning of a cracking catalyst, and
they also contribute to gum formation in finished products.
• The nitrogen compounds in crude oils may be classified as basic or
non-basic.
• Basic nitrogen compounds consist of pyridines. Non-basic nitrogen
compounds, are generally of pyrrole types.
3. Asphaltenes (non polar)
• Heaviest fractions are asphaltenes and resins
• No definite melting point
• Leave carbonaceous residue on heating.
• Structure of condensed polynuclear aromatic layers linked by
saturated links. contribute to
• Contribute to gravity and viscosity increases of crude oils
4.Resins (Polar)
• Molecular weight range of 500–1000
• The resin molecules surround the asphaltene clusters (micelles) and
suspend them in liquid oil
• Insoluble in liquid propane but soluble in n-heptane
5. Metals
• Part of the metallic constituents of crude oils exist as inorganic water-
soluble salts, mainly as chlorides and sulphates of sodium, potassium,
magnesium and calcium.
• Zinc, titanium, calcium and magnesium appear in the form of
organometallic oil soluble.
• Vanadium, nickel, copper and iron are present as oil-soluble
compounds, capable of complexing with pyrrole compounds
• They cause poisoning to the catalysts used for hydroprocessing and
cracking.
Product Fractions
Non Condensable gases (< 20 )
• Low-boiling products encompasses the compounds that are in the gas phase at ambient
temperatures and pressures: methane, ethane, propane, butane, and the corresponding
olefins
• Methane (C1) is usually used as a refinery fuel, but can be used as a feedstock for
hydrogen production by pyrolytic cracking and reaction with steam.
• Ethane (C2) can be used as refinery fuel or as a feedstock to produce hydrogen or
ethylene, which are used in petrochemical processes.
• Propane (C3) is frequently used as a refinery fuel but is also sold as LPG
• The butanes present in crude oils and produced by refinery processes are used as
components of gasoline and in refinery processing as well as in LPG.
• Normal butane (nC4) has a lower vapor pressure than isobutane (iC4) and is preferred
for blending into gasoline to regulate RVP of gasoline.
• Isobutane has its greatest value when used as a feedstock to alkylation units to form
high-octane iso-paraffin compounds in the gasoline boiling range
Naphtha
• It has an initial boiling point (IBP) of about 35 °C and a final boiling point (FBP) of about
200 °C, and it contains paraffins, naphthenes and aromatic hydrocarbons ranging from
those containing 4 carbon atoms to those containing about 10 or 11 carbon atoms.
• The overhead liquid distillate from CDU is called virgin or straight-run naphtha and that
distillate is the largest source of naphtha in most petroleum refineries.
• The virgin naphtha is often further distilled into two streams:
1. virgin light naphtha with an IBP of about 30 °C and a FBP of about 145 °C containing
most (but not all) of the hydrocarbons with six or fewer carbon atoms
2. virgin heavy naphtha containing most (but not all) of the hydrocarbons with more than
six carbon atoms. The heavy naphtha has an IBP of about 140 °C and a FBP of about 205 °C.
• The virgin heavy naphtha is usually processed in a catalytic reformer
• The light naphtha has molecules with six or fewer carbon atoms—which, when
reformed, tend to crack into butane and lower molecular weight hydrocarbons that are
not useful as high-octane gasoline blending components
Gasoline
• Gasolines are complex mixtures of hydrocarbons, having typical boiling ranges from 38 to 205°C
• Components are blended to promote high antiknock quality, ease of starting, quick warm-up, low tendency to
vapor-lock, and low engine deposits.
• Some important streams include:
1. Straight Run Naphtha – once commercially used. Not used much now due to low octane rating. Low in
aromatics and paraffins usually contain more of naphthenes and virtually no olefins. Usually blended upto 20 %
2. Catalytic cracked naphtha - produced with a catalytic cracker, has a moderate octane rating, high olefin content
and moderate aromatic content.
3. Isomerate- isomerizing low-octane straight-run naphtha into Isoparaffins. Isomerate has no aromatics or olefins.
4. Alkylate - alkylation unit, using isobutane and olefins as feedstocks. Finished alkylate contains no aromatics or
olefins
5. Hydrocrackate -produced with a hydrocracker, has a medium to low octane rating and moderate aromatic levels
6. Butane – To usually maintain RVP (nC4can be added to gasoline without exceeding the RVP of the gasoline
product
Kerosene
• Kerosene is a light petroleum distillate (204-300 °C)
• This Kero fraction must meet a flash point specification after it has been steam
stripped, and its end cut point is usually set to meet a smoke point specification.
• Its flash point (the temperature at which it will generate a flammable vapor near
its surface) is 38 °C (100 °F) or higher, whereas that of gasoline is as low as −40 °C
(−40 °F). This property makes kerosene a relatively safe fuel to store and handle.
• The two basic types of jet fuels are naphtha and kerosene.
• Naphtha jet fuel was produced primarily for the military and was a wide boiling-
range stock that extended through the gasoline and kerosene boiling ranges
• Jet fuel is blended for use by both commercial aviation and military and the
primary source of jet fuel blending stocks is the straight-run kerosene from CDU.
Gas Oil and Fuel Oil (Upto o
450 C )
• Usually refers to distillate fuels that are heavier than naphtha and kero fractions
Number 1 fuel oil is a volatile distillate oil intended for vaporizing pot-type burners.It is the
kerosene refinery cut that boils off immediately after the heavy naphtha cut used for gasoline.
Former names include: coal oil, stove oil, and range oil.
Number 2 fuel oil is a distillate home heating oil Trucks and some cars use similar diesel fuel with a
cetane number limit describing the ignition quality of the fuel. Both are typically obtained from the
light gas oil cut.
Number 3 fuel oil was a distillate oil for burners requiring low-viscosity fuel.
Number 4 fuel oil is a commercial heating oil for burner installations not equipped with preheaters.
It may be obtained from the heavy gas oil cut.
Number 5 fuel oil is a residual-type industrial heating oil requiring preheating to 77–104 °C for
proper atomization at the burners. Usually a blend of residual oil with enough number 2 oil to
adjust viscosity until it can be pumped without preheating.
Number 6 fuel oil is a high-viscosity residual oil requiring preheating to 104–127 °C . Could be used
as ship fuel based on user specifications. Heavier fractions are sent to the vaccum tower for futher
distillation
Properties of Crude oil
Crude Assay
The complete and definite analysis of a crude oil is called crude assay.
A complete crude assay will contain some or all of the following:
1. Whole crude gravity, Viscosity, ‘S’ content, pour point etc.
2. TBP curve, Mid Volume plot of gravity, Viscosity etc.
3. Light end analysis up to C8 and C9.
4. Properties of fractions. (naphtha, middle distillates, gas oil residue).
5. Yield vs Vol.%, gravity, S, viscosity, octane no., diesel index, Flash point , Fire
point, Smoke point, Pore point, Vapor Pressure etc.
6. Properties of lube distillates ( if suitable)
7. Properties of asphalt.
8. EFV curve run at atm. Pressure.
Purpose of Characterizations
• Trading: Density,API Gravity
• Transportation: RVP,Pour Point,KV,Wax content
• Contamination: Salt content,BS&
• Processability: Sulfur,Nitrogen,TAN,Asphaltene,MCR
• Cracking Point: ASTM Distillation
• LPG Potential: Light hydrocarbons(GC)
• Classification: Characterization factor
1. API Gravity (ASTM D1298)
• Low dense – High API
• High Dense – Low API
• Usually used for magnification of crude oil densities
• Initially measured using a hydrometer
• Also aromatics are correlated to API. The more the Aromatics lower is the
API
• Based on API (subject to Change): API >31.1 – Light Crude Oil
22.3< API <31.1 – Medium Crude
22.3<API<10 – Heavy crude
API<10 – Extra Heavy
2. Reid Vapor Pressure (ASTM D323)
• Absolute vapor pressure measured at 37.8 °C
• Usually used for all light and medium distillates except LPG
• Sample is cooled to 1 °C and then poured . If sample solid at this temp
then RVP is not measured
• Used to represent volatilization at atm pressure
• Mainly used for motor testing for winter starting and vapor lock cases
for motor fuels
• The True Vapor Pressure (TVP) is measured at vapor liquid equilibrium
and small amount of vaporization is observed.
• Mainly determines the storage facility design.
3. Viscosity (ASTM D88)
• Primarily measured using Saybolt Viscometer
• It is measured as time required in seconds, for efflux of oil of 60 cc
volume through a calibrated orifice
• Usually correlations exist between API gravity and the viscosity
• For lube oils (based on a scale of 100) a viscosity index measures the
viscosity changes with respect to temperature
4. Cloud Point
• Used to estimate the relative amount of paraffin in crude oil
• A high cloud point is indicative of high paraffin content
• Many procedure exist to determine it and procedures do change
• Usually the oil is cooled gradually to a temperature of 30° F below
approximate cloud point and the first incidence of cloudiness is
reported
• Indirectly determines the requirement of tank heaters and coils
5. Pour Point (ASTM D97 and D5949 (Automatic) )
• Initially the specimen is allowed to cool to precipitate wax crystals
• This is followed by heating to a temperature of 9°C above expected
pour point and for every subsequent 3 °C the jar is removed and
tilted and held horizontally for 5 seconds.
• The same is repeated till the sample shows indication of flow.
• This temperature is defined as pour point
• Used to characterize petroleum flow and nozzle heating and pipe
tracing
6. Flash and Fire Point (ASTM D92)
• The flash point of a volatile material is the lowest temperature at which vapours of the material
will ignite, when given an ignition source.
• At the flash point more vapor may not be produced rapidly enough to sustain combustion
• Fire point is higher than the flash point
• The fire point of a fuel is the lowest temperature at which the vapour of that fuel will continue to
burn for at least 5 seconds after ignition by an open flame of standard dimension
• Ignition source temperature is far higher than either the flash or fire point
• The flash point is a descriptive characteristic that is used to distinguish between flammable fuels
• Fuels which have a flash point less than 37.8 °C (100.0 °F) are called flammable, whereas fuels
having a flash point above that temperature are called combustible
• Used in vent sizing calculations for storage tank design
• In general the fire points can be assumed to be about 10 °C higher than the flash point
7. Aniline Point (ASTM D611)
• Defined as the minimum temperature at which equal volumes of aniline and lubricant oil
are miscible, i.e. form a single phase upon mixing..
• The value gives an approximation for the content of aromatic compounds in the
• The lower the aniline point, the greater is the content of aromatic compounds in the oil.
• The aniline point serves as a reasonable proxy for aromaticity of oils consisting mostly of
saturated hydrocarbons
• Equal volumes of aniline and oil are stirred continuously in a test tube and heated until
the two merge into a homogeneous solution.
• Heating is stopped and the tube is allowed to cool.
• The temperature at which the two phases separate out is recorded as aniline point.
• The test indicates if an oil is likely to damage elastomers (rubber compounds) that come
in contact with the oil.
8. Smoke point ( ASTM 1322-97)
• The smoke point is the maximum flame height in millimeters at which
kerosene will burn without smoking, tested under standard
conditions
• The smoke point is related to the hydrocarbon type composition of
such fuels. Generally the more aromatic the fuel the smokier the
flame, for paraffins being least smoky
• Correlations exist to determine based on PNA analysis
• Determining smoke point of kerosene one of the important
properties that should be defined to classify the kerosene quality
9. Total Acid Number (TAN)
• Defined as milligrams of caustic potash required to neutralize acids in
1 g of oil
• Crude is defined as acidic if TAN > 0.5
• Based on amount of sulphur TAN is correlated to : low API, low
solidification point , High nitrogen, heavy metals , asphalt and gel
content
• A high TAN causes naphthenic corrosion significant at high
temperatures (220°C)
10. Micro carbon residue
• To determine the amount of carbonaceous residue formed after evaporation and
pyrolysis of petroleum materials under certain conditions.
• The test is used to provide some indication of a material's coke-forming tendencies
• A quantity of sample is weighed, placed in a glass vial, and heated to 500 °C. Heating is
performed in a controlled manner, for a specific period of time, and under an inert
(nitrogen) atmosphere .
• The sample experiences coking reactions, with volatiles formed being swept away by the
nitrogen.
• The carbonaceous residue remaining is reported as a mass percent of the original
sample, and noted as “carbon residue (micro).”
• For fluid catalytic cracking units, the MCR of the feed can be used to estimate the feed's
coke-forming tendency
• MCR correlates approximately with combustion chamber deposits for diesel
11. Asphaltene content
• Usually the sample is distilled
under vacuum conditions till
formation of coke like residue
• Usually measured under SARA
analysis
• First, asphaltenes is precipitated
by n-heptane.
• The deasphalted oil called
maltenes is subjected to liquid
chromatography.