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Properties of Crude Oil

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Abstract
Crude oil is a complex mixture containing a large number of closed related compounds
which are controlled initially by the nature of organic matter in the source rock. This
paper discusses the physical and chemical properties of crude oil in an oil industry. It
also focusses on a method for predicting the properties of crude oils such as their
boiling fractions, which comprise selecting a chemical or physical, performance property
or groups of properties of the crude oil or its boiling fractions and creating a training set
from reference samples which contain characteristic molecular species present in the
crude oil or its boiling fractions. The reference samples are subjected to GC/MS analysis
wherein the often-collinear data generated is treated by multivariate correlation
methods. This training set produces coefficients, multiplied by the matrix generated
from a GC/MS analysis of an unknown sample to predict selected properties.

1- Introduction

Modern industry is mainly based on petroleum oil which is non-renewable. However,

as early as 1900, vegetable oils were used in engines as fuel.

1) They have also shown high potentials for alternative uses especially as lubricants.

2) Castor oil is one of the few naturally occurring oils that is nearly a pure compound
and is a very good lubricant used in racing cars and jet engines.

3) Thus, a high potential for the oil from indigenous oil seeds would promote their
commercialization, boost the economy, and improve the environment through
afforestation by planting the oilseed trees. The seeds used in the test were from trees
which mainly grow in the semi-arid areas in most parts of Africa. They included;

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(1) Caldendrin Capones which is an outstanding deciduous tree attaining a height of
15m and is common in the Rift Valley and at the coast in Africa.

(2) Croton Megalosaurus which is a tall timber tree reaching 35 m and common in the
Rift Valley.

(3) Podocarps gracious which is a large evergreen forest tree reaching a height of 25m
and common in the highlands.4) Pittosporum indecorum which reaches a height of
18m and is mainly found in the semi-arid areas in the Rift Valley. The research was
therefore aimed at determining the properties of the crude oils which characterize their
use as potential substitutes for petroleum oil.

Literature Review
BASIC DESCRIPTION OF CRUDE OIL
Unrefined petroleum is a perplexing blend of essentially fluid
hydrocarbons with disintegrated gases and follow measures of
suspended water, inorganic residue

Average crude contains (approximately)

• 84% carbon
• 14% hydrogen
• 1-3% sulfur
• 1% nitrogen
• 1% oxygen
0.1% minerals and salts. (Lord, Nov 19-20, 2014 )

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Property Changes During Handling

Consecutive molding, adjustment, partition, and mixing together advances

moving ceaselessly from the wellhead make material streams that may differ
fundamentally from their underlying wellhead condition.
• “Live oil” at the wellhead contains dissolved gases that will spontaneously evolve
(flash) at ambient pressure conditions.
• "Dead oil" downstream of partition procedures won't streak at surrounding
pressure conditions.
Assortment of elements influence how much an oil is molded and settled for
transport (designing, financial matters, security, administrative).
• Chad Woken (EERC) will expand on this theme in a resulting introduction.
API Gravity & Sulfur
1- API Gravity

An increase in API gravity corresponds to a decrease in specific gravity. Units of API

gravity are °API
API = (141.5/SP.GR)- 131.5

Base on the equation above, sp.gr and API gravity refer to weight per unit volume as
compared to water at 60 ° F.
Crude oils gravity may range from less than 10°API to over 50°API but most crudes fall
in 20-45°API.
API gravity refers to liquid sample at 60 ° F (15.6 ° c).
API gravity are not linear, i.e. cannot be averaged unlike sp. Gravities.
Designation of “light” or “heavy” is based on density
• API gravity is common unit of measure
• ≥ 33°API for “light” oil

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2- Sulphur
The Sulphur content of a fossil oil is very important for variety of reasons. Downstream
processes like chemical change cracking and refinement are adversely full of high
Sulphur contents. throughout associate oil spill, the Sulphur content becomes a health
and safety concern for cleanup personnel. additionally, if high Sulphur oils are burning,
they'll turn out dangerous levels of sulfur dioxide.

The total Sulphur content of oil may be determined by variety of ordinary techniques.
ASTM methodology D 129

Customary take a look at methodology for Sulfur in crude product (General Bomb
Method) is applicable to crude product of low volatility and containing a minimum of
zero.1 mass % Sulphur (ASTM D one29). Sulphur contents from EETD and ESD were
determined employing a Horiba MESA two hundred Sulphur and element analyzer, in
accordance with ASTM methodology D 4294 - customary take a look at methodology
for Sulfur in crude product by Energy-Dispersive X-Ray visible radiation qualitative
analysis. This methodology is applicable to each volatile and non-volatile crude product
with Sulphur concentrations starting from zero.05 to five mass % (ASTM D 4294).

Sulfur content is described as “sweet” or “sour”

▪ General rule
• “Sweet” < 1% total mass sulfur.
• “Sour” > 1% total mass sulfur.
▪ Strategic Petroleum Reserve crude oil quality specifications
• “Sweet” < 0.5% total mass sulfur.
• “Sour” < 1.99% total mass sulfur.

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Relevance of API Gravity & Sulfur

Higher API gravity “lighter” oils tend to exhibit
▪ Lower viscosity, flow better for production and transport
▪ Lower average molecular weight
▪ More “light ends” hydrocarbons
▪ Greater volatility.
Tight Oils
Oil created from low-penetrability repository rock.
Commonly animated with pressure driven breaking to deliver at monetary rates.
(Lord, Nov 19-20, 2014 )

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3- Water Content
Some of the oil samples received by ESD contain substantial amounts of water. as a
result of any method that will separate the oil and water would additionally amendment
the composition of the oil, most properties were determined on the oils as received.
Exceptions are noted within the individual information tables. Therefore, for those oils
with important water contents (>5%), several of the properties measured don't represent
the properties of the ‘dry’ oil.

At ESD, water contents were determined by Karl Fischer volumetric analysis employing
a Metrohm 701 KF Automatic apparatus. For additional details, see Appendix one.

4- Flash point
The flash point of a fuel is that the temperature to that the fuel should be heated to
provide a vapor/air mixture on top of the liquid fuel that's burnable once exposed to
associate open flame below nominative take a look at conditions. In North America,
flash purpose is employed as associate index of fireplace hazard. As such, shipping
rules use flash purpose as a criterion to ascertain labelling necessities.

Flash point is an especially necessary consider regard to the security of spill cleanup
operations. Gasolines and alternative lightweight fuels may be kindled below most
close conditions and thus create a significant hazard once spilled. Several freshly
spilled crude oils even have low flash points till the lighter elements have gaseous or
distributed.

There are many ASTM strategies for activity flash points, victimization either closed
cup or open cup testers. Open cup strategies can usually turn out results that are
beyond those measured with closed testers, and will not be used with volatile
substances. The flash points of lubricating oils may be determined by ASTM

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methodology D 92/IP thirty-six customary take a look at methodology for Flash and
hearth Points by Cleveland Open Cup (ASTM D 92).

For determinant the flash points of alternative oils, strategies D 93/IP thirty-four -
customary take a look at strategies for Flash purpose by Pesky-Martens Closed take a
look after and D fifty-six - customary Test methodology for Flash purpose by Tag
Closed Tester are the foremost usually used. The Pesky-Martens tester has associate
integral stirrer, however no cooling tub. The minimum flash point which will be
determined by methodology D93/IP34 is 10°C (ASTM D 93). The Tag closed tester has
associate integral cooling tub, however no stirring mechanism. Methodology D fifty-six
is meant for liquids with a consistency but nine.5 CST at 25°C (ASTM D five6).

Many contemporary crude oils have flash points below 10°C and/or viscosities on top
of nine.5 CST at 25°C. For this reason, at ESD, a Sur BERLIN TAG two automatic
flash purpose tester that has been changed by adding a stirring mechanism is
employed to work out flash points. The mechanism operates during a similar fashion to
a Pesky-Martens tester, however is of a additional economical style. The stirrer aids in
manufacturing additional uniform heat transfer to oils that exceed the look consistency,
and in no method interferes with the take a look at mechanism. Flash points measured
by this instrument are usually repeatable to ±4°C. For additional details, see Appendix
one.

In the information section, flash points taken from the literature, and determined by
open cup strategies are selected by a footnote. No designation is provided if the take a
look at methodology was closed cup or not nominative.

CRUDE OIL PHASE BEHAVIOR

An essential inspiration for this examination is understanding the fire and blast dangers
related with inadvertent arrival of raw petroleum in the vehicle condition.

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▪ It is the fume discharges from a "combustible fluid" that really copy.
▪ Settled rough is ordinarily tried, moved, and sold in the fluid stage and related fume
misfortunes during dealing with and transport, assuming any, are not all around
described.
▪ Fume misfortunes, assuming any, may not cause quantifiable money related effect
from a business viewpoint however could prompt raised hazard from a risks point
of view.

It is accordingly judicious to look at the stage conduct of unrefined, explicitly the

potential for development of fume stage discharges, so as to comprehend the
conditions that add to fire and blast risks around spills.

What is Phase Behavior?

Stage conduct portrays what stages (strong, fluid, gas) are available under certain
thermodynamic ((P) pressure, ( ) explicit volume, (T) temperature) conditions.

• Crude oil can also exhibit very complex phase behavior with multiple solid
phases (asphaltenes, waxes) or supercritical fluids.

Unrefined oils applicable to this investigation at surrounding weight and temperature

can deliver coinciding gas and fluid stages.

Expansion of fire and conceivable catching of unrefined inside a pressurized vessel

(for example railcar brimming with oil presented to pool fire) will broaden significant
parameter space from straightforward surrounding conditions.

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Research Goal
• To describe physical properties of crude oil relevant to flammability and
transport safety.
The vapors (not liquid) from a flammable liquid actually burn, so
understanding what leads to vapor formation during handling, transport
and spill scenarios is key to understanding the flammability risks.
• Identifying crude oil chemical and physical properties (including the
possible presence of nitrogen and/or other "inerts") that could contribute
to increased likelihood and/or severity of handling/transport-related
combustion events.
• Identifying well-site crude oil conditioning system operational parameters
that impact transport safety-critical properties.
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• To improve QA/QC (Quality Assurance & Quality Control) associated
with the understanding of crude oil vapor pressure measurements
necessary for characterizing volumes and compositions of gases that
are likely to evolve from crudes in transport spill scenarios.
The way in which these properties will relate to fire and explosion hazard is the
key research question we need to address. (Lord, Nov 19-20, 2014 ).

Results and Discussion

Density

Podocarpus gracilior had the highest density of 943.9kg/m3 whereas Pittosporum

vindiflorum had the lowest value of 913.7kg/m3 at 298K. The density of the oils was not
affected by the methods of extraction but decreased linearly with increase in temperature
and was well expressed by the equation

below. For oil k; ρk=AkT+Dk (7) where ρk is density (kg/m3), T is absolute temperature
(K), and Dk (kg/m3) and Ak (kg/ m3K) are oil dependent constants. The value for Ak was
almost the same for all the oils. A constant value of -0.65 was used for all the oils and
resulted in a high correlation coefficient (r2) as shown in Table 2. Thus equation (7)
becomes; ρk=-0.65T+Dk (8) Figure 2 shows the graph for the experimental and
calculated values for some of the oils. The lines drawn are for the calculated average
values for POD, CAL and DIE. The densities of the oils were within the recommended
ranges for diesel engine fuels (750950) kg/m3, lubricants (800-1005) kg/m3, hydraulic
fluids (800-1500) kg/m3 and brake fluids (800-1060) kg/m3.162 Journal of the Japanese
society of agricultural machinery Vol.

Viscosity

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The kinematic viscosity of the oils decreased exponentially with increase in
temperature Podocarpus gracilior had the lowest value of about 45.1mm2/s whereas
Pittosporum indecorum had the highest value of 165.5mm2/s at 298K. The lines drawn
are for the calculated average values for CAL, POD, and DIE respectively. The
regression curve for the experimental data was well fitted by equation (9) based on the
general exponential equation for viscosity of fluids. For oil k;(9) where νk (mm2/s) is
kinematic viscosity, T(K) is absolute temperature and Ak(mm2/s), βk(K), and Ck(K)are
oil dependent constants which were high for oils with high kinematic viscosity. For the
temperature range used, the values for Bk and Ck were almost the same for all the
oils. Constant values of 0.25 and 170 were used respectively and resulted in a high
correlation coefficient (r2) as shown in Table 2. Thus equation (9) becomes;(10) ◇
CAL▲ CRO* POD○ PIT+ SUN□ DIE

Methods of extraction showed no significant effect on the viscosity of the oils. The
viscosity index of the oils ranged from 136 for PIT to 176 for POD. Thus, the rate of
change of viscosity with temperature was relatively low for the indigenous vegetable
oils. The kinematic viscosities of the oils were outside the recommended range for
diesel engine fuel (1.5-5.5) mm2/s, hydraulic fluids (13-54) mm2 /s, and brake fluids (6-
7) mm2/s but were within the recommended range of 19-3140mm2/s for lubricants.
The viscosity index of the oils was within the recommended range for lubricants (76-
150).

Thermal Properties

(1) Calorific Value For fuels, one of the other important parameters is calorific value since
it rates the oil's ability to produce enough energy after combustion to run the engine. For
the oils

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tested, Podocarpus gracilior had the highest value of about 41.1MJ/kg whereas
Pittosporum vindiflorum had the lowest value of about 39.1MJ/kg. The values obtained
were generally slightly high compared to the calorific value of sunflower oil (39.7MJ/kg)
but slightly low compared with diesel oil (44.4 SHITANDA, NISHIYAMA, MUTULI):

Properties of Crude Oil from Indigenous Oilseeds in Africa* 163MJ/kg). However, the
values obtained were within the recommended range of 39-46MJ/ kg for diesel engine
fuel.5) Methods of extraction had no significant effect on the calorific value of the oils.

Specific Heat

The oils had generally low specific heat of about 2kJ/kgK and methods of extraction had
no significant effect on it. The values obtained were within the limits for lubricants (1.5-
2.0) kJ/kgK and hydraulic fluids (0.81.5) kJ/kgK.

Thermal Conductivity

The thermal conductivity of the oils ranged from 1.3kJ/mhK for Caldendrin Capones
extracted chemically to 5.8kJ/mhK for Croton Megalosaurus extracted mechanically.
The values obtained were within the recommended range for lubricants and hydraulic
fluids. There was no general trend on the effect of methods of extraction on the thermal
conductivity of the oils since both the chemically and mechanically extracted oils had
low and high values.

Flash Point

The flash point values obtained were high compared with that of diesel especially for
the mechanically extracted oils. Croton Megalosaurus extracted mechanically had the
highest value of 520K whereas Podocarpus gracilior had the lowest value of 301K. The
methods of extraction had significant effect on the flash point of the oils (Figure 4). The
flash point for the chemically extracted oils were generally within the recommended
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range of 323-353K for diesel fuel, 333-573K for lubricants, and 372-541K for hydraulic
fluids. Only Croton Megalosaurus extracted chemically had its flash point within the
recommended range of 393-453K for brake fluids. All the mechanically extracted oils
had flash points within the recommended range for lubricants.

Chemical Properties

❖ Ash Content

The oils showed varied values of ash content which were significantly affected by the
methods of extraction. Caldendrin Capones extracted mechanically had the lowest value
of 0.008% compared to 0.42% for Pit

❖ pH Value

Since the degree of alkalinity or acidity is critical due to wear and corrosion, the pH value
of the oils is an important factor. The oils tested were slightly acidic with pH values of
over 5.0. However,

Caldendrin Capones extracted mechanically had a low pH value of about 3.7. Thus, the
pH values of the oils were generally within the recommended range of 6.5-8 for diesel
fuel and 7-12 for hydraulic fluids.

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5-Conclusion
The indigenous vegetable oils showed a high potential for use in various application
based on the properties obtained. For use as fuel in diesel engine, the oils had relatively
high calorific values and their high viscosity could easily be reduced through increase in
temperature. The high flash point for the mechanically extracted oils and high ash
content for the chemically extracted oils can be overcome by considering the method of
extraction, refining of the oil and through esterification. The oils have also a high potential
for use as lubricants for various applications ranging from motor oil to gear oil as
recommended by Lansdown. Their potential for use as hydraulic and brake fluids is low
based on the determined parameters. Further research on quality and the actual
performance test is recommended. The cetane rating, Sulphur content, carbon content,
smoke point, fatty acid content, and pour point.

References
(Lord, Nov 19-20, 2014 )

Pugh, B. and J. M. Court: Fuels and Lubricating Oils for Internal Combustion Engines. Sir
Isaac Pitman & Sons Ltd, 1955
Peterson, C. L.: Vegetable Oils as Diesel Fuel. Status and Research Priorities. Trans.
ASAE. 29 (5), 1986 3) Pugh, B.: Practical Lubrication. An Introductory Text. Butterworth
and Co. Publisher LTD, 1970
Noad, C. T. and A. Birnie: Trees of Kenya. Published by T. C. Noad and A. Birnie, 1989
Perry, H. R, W. D. Green, and O. J. Maloney: Perry's Chemical Engineers Handbook.
MacGraw-Hill Book Co. 50th Edition, 1984
Mohsenin, N. N.: Thermal Properties of Agricultural Materials. Gordon and Beach Science
Publishers Inc.

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