Physical properties
Thermal properties
Electrical properties
Optical properties
Chromatographic techniques
Spectroscopic methods (Principles and
Applications of UV-Visible, IR, and NMR
Spectroscopy)
Petroleum exhibits a wide range of physical properties and several
relationships can be made between various physical properties.
Whereas properties such as viscosity, density, boiling point, and
color of petroleum may vary widely, the ultimate or elemental
analysis varies, as already noted, over a narrow range for a large
number of petroleum samples. The carbon content is relatively
constant, while the hydrogen and heteroatom contents are
responsible for the major differences between petroleum samples.
Coupled with the changes brought about to the feedstock
constituents by refinery operations, it is not surprising that
petroleum characterization is a monumental task.
Petroleum assay is an investigative (analytic) procedure
in laboratory for qualitatively assessing or quantitatively measuring
the presence or amount or the functional activity of a target entity
(the analyte).
Thus, analyses are performed to determine whether each batch of
crude oil received at the refinery is suitable for refining purposes.
The tests are also applied to determine if there has been any
contamination during wellhead recovery, storage, or transportation
that may increase the processing difficulty (cost). The information
required is generally crude oil dependent or specific to a particular
refinery and is also a function of refinery operations and desired
product slate. To obtain the necessary information, two different
analytical schemes are commonly used and these are: (1) an
inspection assay and (2) a comprehensive assay
Inspection assays usually involve determination of several key
bulk properties of petroleum (e.g., API gravity, sulfur content, pour
point, and distillation range) as a means of determining if major
changes in characteristics have occurred since the last
comprehensive assay was performed.
On the other hand, the comprehensive (or full) assay is more
complex (as well as time consuming and costly) and is usually
performed only when a new field comes on stream, or when the
inspection assay indicates that significant changes in the composition
of the crude oil have occurred. Except for these circumstances, a
comprehensive assay of a particular crude oil stream may not be
updated for several years. A full petroleum assay may involve at least
determinations of (1) carbon residue yield, (2) density (specific
gravity), (3) sulfur content, (4) distillation profile (volatility), (5)
metallic constituents, (6) viscosity, and (7) pour point, as well as any
tests designated necessary to understand the properties and behavior
of the crude oil under examination.
Recommended Inspection Data Required for Petroleum and Heavy Feedstocks (Including Residua)
Petroleum Heavy Feedstocks
Density, specific gravity Density, specific gravity
API gravity API gravity
Carbon, wt.% Carbon, wt.%
Hydrogen, wt.% Hydrogen, wt.%
Nitrogen, wt.% Nitrogen, wt.%
Sulfur, wt.% Sulfur, wt.%
-Nickel, ppm
-Vanadium, ppm
-Iron, ppm
Pour point Pour point
Wax content
-Wax appearance temperature
Viscosity (various temperatures) Viscosity (various temperatures)
Carbon residue of residuum Carbon residue
-Ash, wt.%
Distillation profile: Fractional composition:
-All fractions plus vacuum residue -Asphaltenes, wt.%
-Resins, wt.%
-Aromatics, wt.%
-Saturates, wt.%
Characterization of medium and heavy crude oils using thermal
analysis techniques :
Vacuum Resid
Atmospheric Resid
Crude Oil
Gas Oil
Jet Fuel/Diesel
Gasoline
LPG
Average Carbon Number (Atoms per Molecule)
Petroleum Hydrocarbon
Boiling Range (°C) Boiling Range (°F)
Fractions Range
Of the data that are available, the proportions of the elements in petroleum
vary only slightly over narrow limits:
• Carbon 83.0 to 87.0%
• Hydrogen 10.0 to 14.0%
• Nitrogen 0.1 to 2.0%
• Oxygen 0.05 to 1.5%
• Sulfur 0.05 to 6.0%
• Metals (Ni and V) <1000 ppm
DENSITY AND SPECIFIC GRAVITY :
The density and specific gravity of crude oil are two properties that have
found wide use in the industry for preliminary assessment of the character and
quality of crude oil.
The specific gravity of petroleum usually ranges from about 0.8 (45.30 API) for
the lighter crude oils to over 1.0 (less than 100 API) for heavy crude oil and
bitumen.
One percent by weight solids in the sample can raise the density by 0.007
g/cm3.
VISCOSITY :
Viscosity is the force in dynes required to move a plane of 1 cm2 area at a
distance of 1 cm from another plane of 1 cm2 area through a distance of 1 cm
in 1 sec.
In the early days of the petroleum industry, viscosity was regarded as the body
of petroleum, a significant number for lubricants or for any liquid pumped or
handled in quantity.
SURFACE AND INTERFACIAL TENSION :
The gross heats of combustion of crude oil and its products are given
with fair accuracy by the equation:
Q = 12,400 - 2100d2
The refractive index is the ratio of the velocity of light in a vacuum to the
velocity of light in the substance. The measurement of the refractive index is
very simple, requires small quantities of material, and, consequently, has found
wide use in the characterization of hydrocarbons and petroleum samples.
The refractive and specific dispersion, as well as the molecular and specific
refraction, have all been advocated for use in the characterization of petroleum
and petroleum products. The refractive dispersion of a substance is defined as
the difference between its refractive indices at two specified wavelengths of
light. Two lines, commonly used to calculate dispersions are, the C (6563 Å, red)
and F (4861 Å, blue) lines of the hydrogen spectrum. The specific dispersion is
the refractive dispersion divided by the density at the same temperature:
Specific dispersion = nF – nC/d
This equation is of particular significance in petroleum chemistry because all the
saturated hydrocarbons, naphthene and paraffin, have nearly the same value
irrespective of molecular weight, whereas aromatics are much higher and
unsaturated aliphatic hydrocarbons are intermediate.
OPTICAL ACTIVITY :
The occurrence of optical activity in petroleum is universal and is a general
phenomenon not restricted to a particular type of crude oil, such as the paraffinic or
naphthenic crude oils. Petroleum is usually dextrorotatory, that is, the plane of
polarized light is rotated to the right, but there are known leavo-rotatory crude oils,
that is, the plane of polarized light is rotated to the left, and some crude oils have
been reported to be optically inactive. Examination of the individual fractions of
optically active crude oils shows that the rotatory power increases with molecular
weight (or boiling point) to pronounced maxima and then decreases again. The
rotatory power appears to be concentrated in certain fractions, the maximum lying at
a molecular weight of about 350 to 400; this maximum is about the same for all crude
oils. The occurrence of optically active compounds in unaltered natural petroleum has
been a strong argument in favor of a rather low temperature origin of petroleum from
organic raw materials.
A magnetic field causes all liquids to exhibit optical rotation, usually in the same
direction as that of the magnetizing current; this phenomenon is known as the
Faraday effect, θ and it may be expressed by the relation:
θ = pth
θ is the total angle of rotation, t is the thickness of substance through which the light
passes, and h is the magnetic field; the constant p is an intrinsic property of the
substance, usually termed the Verdet constant (minutes of arc/cm per G); there have
been some attempts to use the Verdet constant in studying the constitution of
hydrocarbons by physical property correlation.
GAS CHROMATOGRAPHY :