Composition of Crude Oil

Classifications of Crude Oil

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Composition of Crude Oil

Crude oil is a natural multicomponent mixture. Its major part is composed of hydrocarbons (alkanes, naphthenes,
and aromatics). Their content in oils ranges between 30% and 100%. Most important among the non-hydrocarbon
components are resins and asphaltenes. The other non-hydrocarbon compounds are metalpo- rphyrin
complexes and trace elements; their content is usually low. Some compounds in oils lost structural features of the
parent organic matter, whereas some other molecules preserved these features. They are called relic
hydrocarbons or chem- ical fossils. Alkane hydrocarbons (C5 C40) include normal and
branched molecules (isoprenoids). Carbon number distribution in the normal alkanes reflects the compo sition of
the original organic matter. For example, lipids of the continental biomass are dominated by normal C25 C33
alkanes that consequently are inherited by the oil. The pristane/phytane ratio is used as a genetic criterion for the
isoprenoids. The pristane is associated with the continental deposits, whereas the phytane is associated with the
marine deposits. Cyclic paraffins (naphthenes) include monocyclic (56 carbon atoms) as well as polycyclic
molecules. The latter molecules may contain 16 rings. This feature was probably inherited from the parent
organic matter (naphthene index). But most polycyclic naphthenes (such as steranes) were not present in the
parent organic matter and have been formed during catagenesis (Petrov, 1984). Arenes (aromatic hydrocarbons)
are usually not as important as the other classes of hydrocarbons in crude oils. Aromatic compounds may include
exclusively aro- matic rings, or may contain complex structures with naphthene rings. Some arenes are directly
related to the parent organic matter. Polishchuk and Yashchenko (2003) showed that there are cyclic changes in
the chemical properties of oils (contents of paraffin, asphaltenes, resins, and sulfur) with geologic age of rocks.
This cyclicity is controlled by the cyclicity of ocean trans- gressions and processes of formation and development
of paleo-oceans in the geological history of the Earth. Recently developed equipment and techniques drastically
increased the information on oil composition. The researchers are now able to determine not only the group
hydrocarbon composition, but also the composition of individual hydrocarbons and their structure. The new
techniques include gas and liquid chromatography, spectral and isotope methods, and nuclear magnetic and
paramagnetic resonances. Among the new highly sensitive equipment are chromatographs, chromato-mass
spectrometers, and infrared, ultraviolet, quasi-linear, and isotope spectrometers. A heightened interest in the
molecular- and atomic-level information on the oil composition was caused by two factors: technological and
geochemical. Petroleum hydrocarbons currently serve as a source of wide spectrum of synthetic substances used
for the manufacturing of various goods in food industry and other industries. This required detailed studies of the
composition of individual hydrocarbons. The current technology provides an opportunity to obtain information

on the detailed composition and structure of hydrocarbons found in the high-boiling oil fractions. Such information
covers carbon atom distribution in the paraffin chains and in the naphthene and aromatic rings. Lately, this
information also became insufficient. The emergence of such analytical techniques as the gasliquid
chromatography and chromato-mass spectrometry enabled scientists to

(1) obtain new information on the composition and structure of petroleum hydrocarbons,
(2) study in detail their homological series, and
(3) determine the distribution patterns of normal and branched alkanes, methylalkanes, and isoprenoid alkanes in
oils.

In studying naphthenes, new techniques led to the elucidation of the proportions of mono-, bi-, tri-, and tetracyclic
naphthenes, steranes and tri-terpanes (hopanes). Detailed studies of aromatic hydrocarbons in crude oils (using
various techniques including spectral) resulted in the establishment of the presence and proportions of not only
mono-, bi-, and tricyclic, but also polycyclic (46 cycles) hydrocarbons that were almost impossible to identify
earlier. The latter include hydrocarbons such as perylene, 1,12-benzoperylene, 3,4-benzopyrene and their
homologes. Nuclear-magnetic and paramagnetic resonance techniques developed in the 1950s enabled to study
the properties of nuclei in different states. This is important in studying the free radicals (kinetically independent),
atoms and atom groups, and chain reactions (polymerization, pyrolysis) in biochemical processes, in which
the free radicals actively participate.
A new approach in studying the crude oil hydrocarbons involves the stereo- chemistry of saturated aliphatic and
alicyclic hydrocarbons. Stereochemical studies of the normal and branched alkanes and mono-, bi-, tri-,
and tetracyclic hydrocarbons (including hopanes) are becoming more important in geochemical studies. It was
shown that the transformations (aging) of biomolecules in the Earths crust is closely related to the changes in
their stereochemistry (Petrov,1984).
There is an increase in the trace element studies. Contents of the trace elements in crude oils vary significantly.
Most of the iron series elements are found in crude oils in amounts below the clarke amounts (sedimentary rock
clarke). Some elements (zinc, nickel, copper, arsenic, and silver) are found in near-clarke amounts, and
fourelements (vanadium, molybdenum, bromine, and mercury) are present in the amounts an order of magnitude
above the clarke. This offers an opportunity of their recovery directly from crude oils. The recovery of trace
elements from crude oils is technically complex and had not been commonly used, althoug scientific
experimentation is in progress.

On the basis of the extensive knowledge of composition and structure for all classes of hydrocarbons, the
presence of biomarkers directly related to the parent biomass had been established. Genetic relationship of crude
oils and parent organic matter, genetic uniformity (or nonuniformity) of oils in different stratigraphic se-
quences have been established. Transformations of the specific hydrocarbons within the catagenetic, weathering,
etc. zones had been elucidated. This information is important in the petroleum exploration as it enables to (1)
forecast the type and composition of hydrocarbon fluids, (2) identify the potential cross-flow zones, and (3)
determine the paths of lateral and vertical migration.

CLASSIFICATION OF CRUDE OILS

Many methods of classification of crude oils have been devised. Systems based on
a superficial inspection involving some physical property, such as specific gravity, are
easily applied and specific gravity is actually used to a large extent in expressing the
quality of crude oils.
Specific weight (or specific gravity) of liquids are compared to that of fresh water
(Table 5.1). For example, if a brine is 1.04 times heavier than fresh water, its specific
gravity is 1.04 and the pressure gradient is equal to 0.45 psi/ft ( 1.04 0.434). The
relationship between the pressure gradient and salt content in water is presented in
Fig. 5.1. If the API gravity of the oil is given, its specific gravity (SG) at 601F can be
determined as follows:

A more rational basis of classification is found in some expression of the composition of the oils. In American
practice, crude oils long have been roughly classified as (a) paraffin base, (b) naphthenic or asphaltic base, and
(c) mixed base if they contain both paraffin and asphalt. (Fig. 5.2). This system was derived on the basis
of differences in the nature of the lubricating oil portion of the crude after a non destructive distillation. In other
words, the crude oil is carefully distilled and the portion boiling in the lubricating oil range is examined. If this
portion is waxy and has the physical properties of paraffins, the crude oil is termed paraffin base. On the
other hand, if the lubricating oil portion contains little or no wax and contains asphaltic material, the crude oil is
termed asphaltic. Crude oils, lubricating oil fraction of which contains both paraffins and asphalts, are termed
mixed base. Using this basis for the classification of petroleum, it has been found that crude oil
occurring in various sections of the United States can also be classified. The Pennsylvania type of crude oil is
paraffinic. This type of crude oil is found in the eastern states of USA: Pennsylvania, West Virginia, New York,
Michigan, and Ohio.