SCE4106: FUNDAMENTALS OF PETROLEUM REFINING

INSTRUCTOR: FORTUNATE OGENE

Master of Technology Chemical Engineering; B.Sc. Petroleum Geoscience and Production
Email: [email protected]

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Characterization or Properties of Petroleum and
its Products

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 Characterization or Properties of Petroleum and its Products

❑ Properties of crude oil and its products are determined based on

established standards like;
o ASTM; American Society for Testing Materials;
o ISI; Indian Standard Institute;
o IP; Institute of Petroleum etc;
i. API gravity:
❑ Density of petroleum oils is expressed in terms of API gravity rather than
specific gravity;
❑ It is calculated from an expression;

❑ Specific gravity; refers to weight per unit volume at 60 oF as compared to

water at 60 oF;
❑ Increase
08/02/2024 in API corresponds to a decrease in specific gravity;
 Characterization or Properties of Petroleum and its Products

i. Reid Vapour Pressure (RVP):

❑ This is used for gasoline;

❑ It is defined as vapor pressure at 100oF (37.8oC) of a product

determined in a volume of air 4 times the liquid volume;

Significance:
o It is an indication of ease of starting and vapor lock tendency of
gasoline as well as explosion and evaporation hazards;
o It is measured in kPa or psig;
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 Characterization or Properties of Petroleum and its Products

ii. Flash point and fire point:

❑ Flash point is the minimum temperature at which the vapours of a
petroleum product form a flash or ignite momentarily with a little flame
passed on the surface;

❑ Fire point is the minimum temperature at which the vapours of a

petroleum product will ignite and sustain the ignition for like 5 seconds
when a little flame is passed on the surface;
Significance:
o Indicates the temperature below which an oil can be handled safely;
o Indication of fire and explosion potential of the products;
o NOTE: Fire point>flash point.
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 Characterization or Properties of Petroleum and its Products

iii. Flash point and fire point: (cont…)

❑ Instruments used include

● Pensky-marten closed cup(D-93)
o used for materials having flash point >148 oF (middle distillates and
fuel oil);
● Tag closed cup (D-56)
o used for materials having flash point between 68- 148 oF (kerosene
& light distillates);
● Cleveland open cup method

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 Characterization or Properties of Petroleum and its Products

iii. Flash point and fire point: (cont…)

❑ Instruments used include

Cleveland open cup method

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 Characterization or Properties of Petroleum and its Products

v. Cloud point and Pour point:

❑ Cloud point and pour point are flow properties of petroleum in cold
temperatures. They are used to determine the extent at which petroleum
products can withstand cold temperatures to flow.

❑ Cloud point of petroleum is the temperature at which paraffin wax or

other solidifiable compounds present in oil appear as a haze when the oil
is chilled under prescribed conditions (ASTM D-2500, D-3117).

Significance:

o Cloud point is used to determine the tendency of small orifice to plug in

cold operating temperature.
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 Characterization or Properties of Petroleum and its Products
v. Cloud point and Pour point: (cont…)
❑ Pour point ; This is the lowest temperature at which the oil stops to flow
under definitely prescribed conditions when it is chilled without
disturbance at standard state (ASTM D-97);

❑ Pour point is determined to be 3 oC above the point at which a sample

can be horizontally held and no movement occurs for 5 sec;

❑ ASTM-5853 used for crude having pour point >-36 oC;

❑ ASTM D-97 used for crudes having pour points <-36 oC;
❑ Low pour points are due to low paraffin content and high aromatics;
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 Characterization or Properties of Petroleum and its Products

v. Cloud point and Pour point: (cont…)

Significance:
o Important for crudes that are transported through pipe lines from
source to load points;
o It’s a measure of the paraffinicity and aromaticity of crude;

❑ Note: pour point<cloud point

v. Freezing point (for jet fuel):

❑ The temperature at which crystal starts to form in hydrocarbon liquids and
then disappear when the liquid is heated is the freezing point;
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 Characterization or Properties of Petroleum and its Products

i. Aniline point (D-611) (for diesel):

❑ This is the minimum temperature at which equal volume of aniline and the
test sample mixes completely;
❑ It is an indication of the paraffinicity of the sample;

❑ Paraffinic hydrocarbons have high aniline points than aromatic

hydrocarbons;
❑ Cycloparaffins and olefins exhibit values between paraffins and aromatics;

Significance:
❑ Aniline point is used as a classification of ignition quality of diesel.
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 Characterization or Properties of Petroleum and its Products

ii. Octane number:

❑ This is defined as the %age by volume of iso-octane that must be mixed
with n-heptane in order to match the knock intensity of the fuel
undergoing testing e.g 90 gasoline matches the knock characteristics of a
blend containing 90% iso-octane and 10% n-heptane.

❑ The two common types of octane numbers determined by the

laboratory tests include :
MON (motor octane number);
RON (research octane number);
❑ The difference between RON and MON i.e (RON –MON) is an
indicator of the sensitivity of the performance of the fuel to the two
types of driving conditions and is known as the sensitivity.
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 Characterization or Properties of Petroleum and its Products

vii. Octane number: (Cont…)

Differences between RON and MON

RON (ASTM D-908) MON (ASTM D-357)

• Engine speed =600 rpm • 900 rpm

• Inlet air temperature= 125 • 300oF

o
F
• Indicates city driving when • High speed performance on
acceleration is frequent high way or heavy load

NOTE: RON>MON
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 Characterization or Properties of Petroleum and its Products

vii. Octane number: (Cont…)

❑ Octane number decreases with increase in the carbon chain i.e

o RON of n-butane>n-pentane>n-hexane>n-heptane;

o Typical values of the RON are 93,62,25 and 0 respectively;

❑ Similarly octane number decreases by varying structure;

o Aromatics>cycloalkane>n-alkane;

o E.g RON of toluene>100 while RON of methyl cyclohexane =75;

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 Characterization or Properties of Petroleum and its Products

viii. Metal content, ppm:

❑ Metals vary from a few ppm to more than 1000ppm;

❑ Metals in crude affects catalyst activity , leads to corrosion and

ultimately lowers the value of product distribution;

❑ Metals in crude are determined by Atomic Absorption Spectroscopy

(A.A.S) and X-ray Fluorescence (XRF);

❑ Metals in crude can be removed by solvent extraction;

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 Characterization or Properties of Petroleum and its Products

x. Nitrogen content (ASTM D-3228 and D-4629):

❑ Determined by chemical luminescence;

x. Sulfur content, wt%:

❑ Sulfur content is expressed as percentsulfur by weight andvaries
from less than 0.1 % to greater than 0.5%;
❑ Measured by x-ray technique (ASTM-D4294) or D5291;
❑ Samples having higher ‘S’ content measured by combustion
technique (ASTM-D1552);Crude oil based on sulphur composition can be
categorized as
○ Sweet crude (S<0.5wt.%)
○ Sour
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 Characterization or Properties of Petroleum and its Products

xi. Total Acid Number (TAN):

❑ No. of mg of KOH required to
neutralize 1g of oil. Typical value of
crude =0.05-6.0;

xii. Smoke point (for kerosene and jet fuel)

❑ This is the height of the flame in
mm beyond which smoking
takes place;
❑ Normally high values represents
clean burning fuel; A diagram of an enclosed wick-fed lamp
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 Characterization or Properties of Petroleum and its Products

xiii. Salt content, lb/1000 bbl:

❑ Crude oil usually contains salt in water thatis emulsified in

solution in water that is emulsified with crude oil;

❑ Salt content is expressed as NaCl in pounds per thousand barrels (PTB)

of crude oil;

❑ Typical value =1-20 PTB (1 PTB~3ppm);

❑ If salt content >10 PTB, necessary to desalt the crude before

processing;
❑ Measured
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 Characterization or Properties of Petroleum and its Products

xiv.Carbon Residue:
❑ This is a measure of the coke forming tendency of crude oil;

❑ Determined by distillation in the absence of air of the sample to

a coke
residue;
❑ Carbon residue is expressed as wt.% of original sample;

❑ Three standard ASTM tests:

o Conrad son residue (ASTM D-189)
o Ramsbottom carbon residue (ASTM D524)
o Micro-carbon residue (ASTM D-4530)
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 Characterization or Properties of Petroleum and its Products

v. Viscosity:
❑Kinematic viscosity is determined by Fenske Redwood,
u-tube, ubbelohde and; Ostwald methods; Engler,
❑ Viscosity units:Centistokes(kinematic viscosity), seconds Saybolt
universal, seconds Saybolt Furol;
❑ Saybolt Universal Viscosity (SUS)(ASTM D88) is the time in seconds
required for the flow of 60ml of petroleum from a container at constant
temperature through a calibrated orifice e.g viscosity of lube oil
measured in seconds Saybolt universal at 100,130 or 210oF;
❑ Saybolt Furol Viscosity (SFS) is determined in a similar manner except
that large orifice is employed;
❑ Fuel oil is measured in seconds Saybolt furol at 1200 or 210oF;
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 Characterization or Properties of Petroleum and its Products

vi. Viscosity index (lubricating oil ):

❑ This is the rate of change of viscosity with temperature;

❑ VI at 100 implies an oil that tend to become viscous at low temperature or

becomes thin at elevated temperature;

❑ Higher VI implies the rate of change of viscosity with temperature is low;

o Paraffinic base lube oil VI~100

o Naphthenic base lube oil VI~40
Paraffinic wax VI~200.
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 Characterization or Properties of Petroleum and its Products

ii. Characterization factors(Kw):

❑ The most commonly used are the UOP and Watson characterization
factors;
❑ Useful in evaluation of individual fraction from crude;

where G = specific gravity at 60oF

TB =Mean average boiling point , oR

o Kw =10.5 for highly naphthenic crude

o Kw=12.9 for paraffinic base crude
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 Characterization or Properties of Petroleum and its Products

viii. Correlation index(CI):

❑ Correlation index CI is useful for evaluating individual fractions
from crude oil;
❑ CI scale is based upon straight chain paraffins having a CI =0 and
benzene CI =100;
❑ Low CI value implies high concentration of paraffin HC and high CI imply
high concentration of naphthenes and aromatics;

xix. Diesel Index (DI)

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 Characterization or Properties of Petroleum and its Products

❑In addition to measuring the bulk properties, crude oil is also characterized
by boiling point fractions.
❑Each fraction can then be analysed for the same properties (%S, API, etc.)
and for appropriate product properties.

❑ We measure the liquid volume

fraction distilled as we increase the
temperature slowly:
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 Characterization or Properties of Petroleum and its Products

❑First fraction to distill is material

that boils typically at less than
40 oC. This is called Light
Ends.

❑Mostly dissolved C1, C2 and C3

compounds.

❑LPG is usually < 4% of crude

oil.
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 Characterization or Properties of Petroleum and its Products

❑The second fraction boils typically between

40 oC and about 90 oC and is known as
light naphtha (sometimes called as gasoline
or straight run gasoline).

o Light naphtha is usually blended straight

into gasoline.
o Light naphtha is usually < 10% of the
crude oil.
o Light naphtha contains mostly paraffins.
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 Characterization or Properties of Petroleum and its Products

❑Between typically 90 oC and about 190 oC,

we get Heavy Naphtha (HN) (sometimes
called naphtha).
o Heavy naphtha can also be blended
into gasoline, but usually requires
upgrading first.
o HN typically about 10 - 20% of the
crude oil.
o HN contains primarily parrafins but significant proportion of
naphthenes and some aromatics.
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 Characterization or Properties of Petroleum and its Products

❑From typically 190 oC to 270 oC, we

get kerosene (sometimes called
straight run kerosene or light
distillate).
● Kerosene goes to make jet fuel,
or can be taken as HN and
diesel.
● Considerably more naphthenes
and aromatics than heavy
naphtha.
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 Characterization or Properties of Petroleum and its Products

❑Between typically 270 oC and 320

o
C, we get D(sometimes called
straight run diesel or heavy
distillate).
❑This goes to make diesel fuel or
heating oil.

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 Characterization or Properties of Petroleum and its Products

❑Between typically 320 oC and 430 oC,

we get heavy gas oil. This can be
blended into heavy fuel oil, but it is
more economically attractive to convert
it to lighter products.
● The oil starts to undergo thermal
decomposition when we get to higher
temperatures.

● To prevent this, we pull a vacuum that

allows us to collect more fraction.
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 THANK YOU

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