SLIDE 2

 Crude Oil” means all kinds of hydrocarbons in liquid form in their natural
state or obtained by Natural Gas by condensation or extraction.
 Crude oil exhibits a wide range of physical properties and several
relationships can be made between various physical properties
 Crude oil or petroleum is a naturally occurring and flammable liquid found
in rock formations in the earth.
 It consists of a complex mixture of hydrocarbons of various molecular
weights.
 Petroleum is a mixture of a very large number of different hydrocarbons; the
most commonly found molecules are alkanes (paraffins), cycloalkanes
(naphthenes), aromatic hydrocarbons, or more complicated chemicals like
asphaltenes, resins etc. Each petroleum variety has a unique mix of
molecules, which define its physical and chemical properties, like colour and
viscosity.

SLIDE 3

 A crude oil assay is essentially the chemical evaluation of crude oil

feedstock by petroleum testing laboratories.

 Each crude oil type has unique molecular chemical characteristics

It is important to determine the physical and chemical characterizations of

crude oil through a crude oil assay, since they are used in different areas in the
petroleum refining industry. The most common applications of petroleum assays
are:
1. To provide extensive detailed experimental data for refiners to establish the
compatibility of a crude oil for a particular petroleum refinery
 2. To anticipate if the crude oil will fulfil the required product yield, quality,
and production
3. To determine if during refining the crude oil will meet environmental and
other standards
4. To help refiners to make decisions about changes in plant operation,
development of product schedules, and examination of future processing
ventures
5. To supply engineering companies with detailed crude oil analyses for their
process design of petroleum refining plants
6. To facilitate companies’ crude oil pricing and to negotiate possible penalties
due to impurities and other non-desired properties.

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SLIDE 8

 With the help of simple fractional distillation we can find the boiling range
of the given sample. Boiling range gives us information on composition, the
properties, and the behaviour of the fuel during storage and use.
 Distillation data helps us characterize the crude oil. By combining
atmospheric and vacuum distillation data, we can get the True boiling point
curve.
  These batch distillation methods allow the collection of a sufficient amount
of distillation fractions to be used for further testing and calculation of
correlation indices and yield percentages.
SLIDE 9

The Correlation index value (CI) is an empirical characterization number which

provides a general estimation of the proportions of hydrocarbon types present in
the distillate fractions of crude oils

 Crude oils can be arbitrarily classified into three or four groups depending
on the relative ratio of the hydrocarbon classes that predominate in the
mixture. The following describes three types of crudes:
1. Paraffinic—the ratio of paraffinic hydrocarbons is high compared to
aromatics and naphthenes.
2. Naphthenic—the ratios of naphthenic and aromatic hydrocarbonsare
relatively higher than in paraffinic crudes.
3. Asphaltic—contain relatively a large amount of polynuclear aromatics, high
asphaltene content, and relatively less paraffins than paraffinic crudes.
Crude oils can be arbitrarily classified into three or four groups depending on
the relative ratio of the hydrocarbon classes that predominate in the mixture.
The following describes three types of crudes:
4. Paraffinic—the ratio of paraffinic hydrocarbons is high compared to
aromatics and naphthenes.
5. Naphthenic—the ratios of naphthenic and aromatic hydrocarbonsare
relatively higher than in paraffinic crudes.
6. Asphaltic—contain relatively a large amount of polynuclear aromatics, high
asphaltene content, and relatively less paraffins than paraffinic crudes.
  Correlation index is a useful criterion for indicating the crude class or type.
The following relationship between the mid-boiling point in Kelvin degrees
(°K) and the specific gravity of a crude oil or a fraction yields the correlation
index as:
𝟒𝟖𝟔𝟒𝟎
𝐂. 𝐈. = + 𝟒𝟕𝟑. 𝟕𝐆 − 𝟒𝟓𝟔. 𝟖
𝐊
 where,
K = mid-boiling point in Kelvin degrees (Mid-boiling point is the
temperature at which 50 vol % of the crude is distilled.)
G = specific gravity at 60/60°F
 A zero value has been assumed for n-paraffins, 100 for aromatics. A low CI
value indicates a higher paraffin concentration in a petroleum fraction.
 The great difference in the amounts of the principle hydrocarbon families
(i.e. paraffins, naphthenes and aromatics) in each boiling point fraction of
various crude oils permits a relatively great degree of differentiation for
correlation purposes.

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SLIDE 12

API stands for American Petroleum Institute. API gravity is the measure of how
heavy of light petroleum liquid is compared to water. It is defined at a reference
temperature of 150C. If its API gravity is less than 10, it is heavier and sinks and
vice versa.
Procedure:

1. Heat the sample to a specific temperature where the sample is sufficiently fluid
and transfer it to hydrometer cylinder.
2. Lower the hydrometer carefully in the hydrometer cylinder avoiding any bubble
formation. Place the thermometer in the cylinder.
3. Release the hydrometer and let it settle.
4. Once the thermometer is in equilibrium, read both the temperature and
hydrometer scale.
5. Correct the hydrometer reading for meniscus effect, thermal expansion and
calibration temperature effects.

SLIDE 13

1. Maintain the bath at the test temperature within the limits given, taking into
account the precautions given.
2. To obtain the most reliable temperature measurement, it is necessary that two
thermometers with valid calibration certificates be used.
3. The thermometers should be held in an upright position under the same
conditions of immersions as when calibrated.
4. Measures should be taken to eliminate parallax error.
5. Select a clean dry, calibrated viscometer having a range covering the estimated
viscosity (that is a wide capillary for a very viscous liquid and a narrower
capillary for a more fluid liquid). The flow time should not be less than 200 sec.
6. When the test temperature is below the dew point, affix loosely packed drying
tubes to the open ends of the viscometer. The drying tubes must fit the design
 viscometer and not restrict the flow of the samples by the pressures created by
the instrument.
7. Carefully flush the moist room air from the viscometer by applying vacuum to
one of the drying tubes.
8. Before placing the viscometer in the bath, draw up the sample into the working
capillary and tuning bulb and allow draining back as an additional safeguard
against moisture condensing or freezing on the walls.

Procedure for measuring dynamic viscosity:

1 .Determine the kinematic viscosity as described.

2. Determine the density of the sample at the same temperature as the viscosity.
3. Note the observed time taken by the fluid.
4. Calculate the kinematic viscosity from the measured flow time and the
instrument constant by the means of this formula

Slide 15

1. Pour the sample into the test jar to the level mark. If necessary, heat the sample
in a bath until it is sufficiently fluid to pour into the test jar.
2. Close the test jar with the cork containing high-pour thermometer. Adjust the
position of the cork and the thermometer so that the cork fits tightly and the
thermometer is co-axial with the jar and the thermometer bulb is immersed well
below the surface of the sample.
3. Heat the specimen without stirring to 9°C above the expected pour point, but to
at least 45°C, in a bath maintained at 12°C above the expected pour point, but at
least 48°C.
4. Transfer the test jar to a bath maintained at 24 +- 1.5°C and commences
observations for pour point. When using a liquid bath, ensure that the liquid
level is between the fill mark on the test jar and the top of the test jar.
5. Before transferring the test jar to the cooling jar, insert the test jar in the jacket.
Never place a jar directly into the cooling medium.
6. Pour points are expressed in integers that are positive or negative multiples of
3°C. Begin to examine the appearance of the sample when the temperature of
the sample is 9°C above the expected pour point (estimated as a multiple of
3°C).
7. At each test thermometer reading that is a multiple of 3°C below the starting
temperature remove the test jar from the jacket.
8. Tilt the jar just enough to ascertain whether there is a movement of the sample
in the test jar. If movement of sample in the test jar is noted, then replace the
test jar immediately in the jacket and repeat a test for flow at the next
temperature, 3°C lower.
9. If the sample in the jar does not show movement when tilted, hold the jar in a
horizontal position for 5 s, as noted by an accurate timing device, and observe
the sample carefully. If the sample shows any signs of movement before 5 s
have passed, replace the test jar immediately in the jacket and repeat a test for
flow at the next temperature, 3°C lower.
10.Continue in this manner until a point is reached at which the sample shows no
movement when the test jar is held in a horizontal position for 5 s. Record the
observed reading of the test thermometer.
The pour point of a petroleum specimen is an index of the lowest temperature
of its utility for certain applications.
Pour Point of petroleum products- the lowest temperature at which movement of
the test specimen is observed under prescribed conditions of test.

Slide 16

To determine the boiling range characteristics of petroleum.

1. Pour a 100ml of sample oil in the distillation flask. Put some boiling chips in
the solutions in case there is an irregular boiling behaviour.
2. Fix the thermometer to the vapour tube using a snug fitting cork. Make sure that
the bulb of the thermometer is in level with the opening to condenser tube.
3. Fit the flask with vapour tube and vapour tube with the condenser tube.
4. Mark the receiving cylinders as 500C, 750C…. etc. till 3000C. Collect the
distillate from starting temperature to 500C in cylinder marked 500C, then 500C
to 750C in the one marked 750C and so on.
5. Place the receiving cylinder at the distillate end.
6. Start heating the flask slowly.
7. Initial Boiling Point:
Notice the temperature on the thermometer when you observe the first drop of
distillate coming out. This is initial boiling point.
8. Final Boiling Point: The maximum temperature reading observed during
distillation. When the residue in the flask is around 5 ml. Control the rate of
increase of temperature and slow it down. Let the condensate collect in the
cylinder completely.
9. Measure the volume of all the fractions collected.
Slide 17

1. Proceed through the distillation process as given in the previous experiment.

2. Collect the samples as directed.
3. Now weigh the specific gravity bottle (W1 gm).
4. Fill it with air free distilled water. Weigh it (W2 gm).
5. Now fill the bottle with distillate fraction and weigh again (W3 gm).
Repeat for all the fractions

In a plot of specific gravity versus the reciprocal of absolute boiling point, stable
hydrocarbons arrange themselves according to their basic structure. The straight
line for normal paraffins has been assigned a correlation value of zero and an
arbitrary value of 100 has been assigned to benzene (Smith1940)
The correlation index criterion is used to indicate group characteristics of different
distillate fractions of crude oil (collected at atmospheric pressure at 25 0C interval
from initial boiling point to 3000C). Correlation of each fraction is calculated by
the formula:
𝟒𝟖𝟔𝟒𝟎
𝐂. 𝐈. = + 𝟒𝟕𝟑. 𝟕𝐆 − 𝟒𝟓𝟔. 𝟖
𝐊
Where,
K is the average boiling point of the fraction
G is the specific gravity 60/600F.
Paraffinic crudes exhibit low C.I. whereas proportions of cyclic compounds cause
the index values to increase.
Also, specific gravity can be calculated using the formula:

𝐖 = (𝐰𝐞𝐢𝐠𝐡𝐭𝐨𝐟𝐨𝐢𝐥)/(𝐰𝐞𝐢𝐠𝐡𝐭𝐨𝐟𝐰𝐚𝐭𝐞𝐫)
Specific gravity calculated from above formula is at room temperature. It should be
converted to the temperature of 150C and then used to calculate the correlation
index.

The plot between correlation indices and the fraction numbers will tell us about the
type of oil it is.

Slide 18

A test portion of the sample is mixed with petroleum ether and the mixture heated
under reflux, and the precipitated asphaltenes, waxy substances, and inorganic
material are collected on a filter paper. The waxy substances are removed by
washing with hot petroleum ether in an extractor. After removal of the waxy
substances, the asphaltenes are separated from the inorganic material by
dissolution in hot toluene, the extraction solvent is evaporated, and the asphaltenes
weighed.
Significance:

Asphaltenes are the organic molecules of highest molecular mass and carbon-
hydrogen ratio normally occurring in crude petroleum and petroleum products
containing residual material. They may give problems during storage and handling
if the suspension of asphaltene molecules is disturbed through excess stress or
incompatibility.
Reagents used:

 Toluene (methylbenzene) [C6H5CH3] - analytical reagent or nitration

grade and Heptane[C7H16] - analytical reagent grade
Procedure:

1. Add petroleum ether in necessary amounts to the test sample taken in a flask
and boil the mixture under reflux for considerable time interval.
2. After this, remove the contents of the flask and allow them to cool for some
time.
3. Using forceps, place the folded filter paper in the filter funnel. Ensure that
there is no loss of asphaltene by creeping.
4. Pour the contents of the flask through the filter and remove the filter paper and
the contents from the funnel and place them in a reflux extractor.
5. Using a flask different from the initial one, reflux with petroleum ether from
the end of the condenser for a timed extraction period until a few drops of
petroleum ether from the bottom of the extractor leave no residue on
evaporation on a glass slide. Continue refluxing until all asphaltene has been
dissolved from the filter paper.
6. Transfer the contents of the flask to a clean and dry evaporating vessel.
10. Wash out the flask with successive quantities of toluene.
11. Remove toluene by evaporation on a boiling water bath.
12. Dry the dish and contents in a oven and then cool in a cooling vessel
and then weigh the contents of the dish carefully.
13. Note the weight of the asphaltene in the sample. Calculate the asphaltene
content, in % m/m, of petroleum products as follows:
𝐌
𝐀 = 𝟏𝟎𝟎( )
𝐆
Where,:
M= is the mass of asphaltenes, in grams, and
G= is the mass of sample, in grams.
Slide 19

To separate and get the amount content of saturates (saturated compounds),

aromatics (aromatic compounds) and NSOs (Nitrogen, Sulphur, and Oxygen)
compounds in the sample.
Column chromatography is basically a type of adsorption chromatography
techniques.

Procedure:

1. The stationary phase material, silica gel is suitably moistened with mobile
phase, petroleum ether and packed sufficiently in the column with a cotton
or pad at the bottom.
2. The sample to be separated is placed on the top of packed stationary phase
with second cotton in between.
3. The mobile phase, petroleum ether is poured into the column over the
sample.
4. A collecting beaker is placed at the bottom of column near the end to collect
the eluted compound, the saturates.
5. After sufficient time interval, the second mobile phase, toluene is poured
into the column.
6. Another collecting beaker is placed at the bottom of column near the end to
collect the eluted compound, the aromatics.
7. The final residue has NSO compounds and resin. The NSO if necessary can
be eluted from the column using methanol as mobile phase.
 8. Thesaturates are eluted with petroleum ether. We distill the solution to get a
concentrated mixture of petroleum ether and saturates. This is allowed to dry
for a day or heated in the oven to get saturates.
9. The aromatics are eluted with toluene. We distill the solution to get a
concentrated mixture of toluene and aromatics. This is allowed to dry for a
day or heated in the oven to get aromatics

Slide 20:

The crude oil sample produced from well number A13 at the depth interval of
2312m - 2318m is taken for characterization study using ASTM standard methods.
Slide 21

The above table shows the density, specific gravity, pour point, kinematic
viscosity, wax content, and resins present in the crude oil sample

Slide 22

The above table shows the distillation data of the crude oil sample taken for
characterization study. And it has been found out that the initial boiling point of the
taken crude oil smaple is 45o C. The paraffinic cuts are eluded in the range of 75o C
to 175o C. The napthenic cuts are eluded in the range of 200 o C to 250oC and the
aromatic compositions cuts are taken in the range of 275o C to 300o C.
Slide23

The above table indicates the composition of crude oil sample taken for
characterization study. And it has been noted that the crude sample has higher
percentage of alkanes/alkenes and aromatic content is at minimum percentage. And
the saturate aromatic ratio is found out to be 2.43
Slide 24
The above table shows the gas chromatographic data for saturate fraction of the
crude oil sample. And it has been found out that the crude sample has nC15
fraction has the maximum percentage.